CN101125473B - Hot-dip galvanized thin steel sheet, thin steel sheet processed by hot-dip galvanized layer, and a method of producing the same - Google Patents
Hot-dip galvanized thin steel sheet, thin steel sheet processed by hot-dip galvanized layer, and a method of producing the same Download PDFInfo
- Publication number
- CN101125473B CN101125473B CN2007101402736A CN200710140273A CN101125473B CN 101125473 B CN101125473 B CN 101125473B CN 2007101402736 A CN2007101402736 A CN 2007101402736A CN 200710140273 A CN200710140273 A CN 200710140273A CN 101125473 B CN101125473 B CN 101125473B
- Authority
- CN
- China
- Prior art keywords
- sheet metal
- steel
- coating
- galvanizing
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Abstract
The present invention provides: a high-strength high-ductility hot-dip galvanized steel sheet and hot-dip galvannealed steel sheet having high fatigue resistance and corrosion resistance; a high-strength hot-dip galvanized steel sheet excellent in ductility, which improves non-plating defects and plating adhesion after severe deformation, and a method of producing the same; a high-strength and high-ductility hot-dip galvanized steel sheet having high fatigue resistance and corrosion resistance; a high-strength hot-dip galvanized steel sheet and hot-dip galvannealed steel sheet having superior appearance and workability, which suppresses the generation of non-plating defects, and a method of producing the same; and a high-strength hot-dip galvannealed steel sheet and a high-strength hot-dip galvanized steel sheet, which suppress non-plating defects and surface defects and have both corrosion resistance, in particular corrosion resistance in an environment containing chlorine ion, and high ductility, and a method of producing the same.
Description
The application submitted on June 6th, 2002, and denomination of invention is divided an application for one Chinese patent application No.02811523.6 (the international application no PCT/JP02/05627's) of " having the high-strength hot-dip galvanized sheet metal of high binding force of cladding material behind fatigue resistance, corrosion resistance, ductility and the severe deformation and the sheet metal and the manufacturing approach thereof of galvanizing by dipping layer DIFFUSION TREATMENT ".
Technical field
Invention relates to galvanizing by dipping sheet metal and the galvanizing by dipping layer of a kind of high strength, the high ductibility sheet metal through DIFFUSION TREATMENT; This steel plate has excellent fatigue resistance and corrosion resistance; Be suitable for construction material, household electrical appliance and automobile, and this steel plate in the chloride ion-containing environment corrosion resistance and excellent workability and relate to and the manufacturing approach of this steel plate.
Technical background
The galvanizing by dipping technology is used for sheet metal and is intended to prevent corrosion, and galvanizing by dipping sheet metal and galvanizing by dipping layer DIFFUSION TREATMENT sheet metal are widely used in building materials, household electrical appliances, automobile etc.Sendzimir (Sendzmir) galvannealing is being followed successively by on the tinuous production as the step that a kind of manufacturing approach comprises: oil removing is cleared up, in non-oxidizing atmosphere, heats sheet metal, is being contained H
2And N
2Reducing atmosphere in sheet metal annealing, be cooled near the coating bath temperature temperature, immerse in the fused zinc groove, and will it cooling or through reheat make it alloying formation Fe-Zn alloy after with its cooling.The Sendzimir processing method is widely used in sheet metal and handles.
As for annealing before plating, usually use full reduction furnace, wherein annealing is right after after the oil removing cleaning, heats the sheet metal operation promptly in containing H without nonoxidizing atmosphere
2And N
2Reducing atmosphere in carry out.In addition, also adopt the flux growth metrhod that comprises following operation: sheet metal is carried out oil removing and pickling; Using ammonium chloride or similar substance to carry out flux then handles; Sheet metal is immersed in the coating bath; Cool off sheet metal then.
At a kind of coating bath that is used for above-mentioned those processing methods, add a small amount of Al and remove the oxygen in the fused zinc.In Sendzimir coating process, zinc-plated liquation contains 0.1% (quality) Al approximately.It is reported that because Al is stronger to the affinity comparison Fe-Zn of Fe in the plating bath, therefore, when steel immersed plating bath, producing one deck Fe-Al alloy-layer also was rich aluminium lamination, thereby has suppressed the Fe-Zn reaction.Because the existence of rich aluminium lamination causes the Al content in the gained coating generally to be higher than the Al content in the plating bath.
Recently, consider that improving durability alleviates body quality with being intended to improve vehicle fuel efficient, the demand of the high strength galvanized sheet metal of excellent processability is increased day by day.Add the Enhancement Method of Si as a kind of economy in the steel, the high ductibility high-strength steel sheet often contains the Si that is not less than 1% (quality) in practice.In addition, high strength steel also contains various alloy, and therefore makes, considers strict restriction heat treatment method to guarantee high-intensity angle from the control microscopic structure.
Moreover, from the angle of plating operation,, use in routine under the situation of the Sendzimir coating process that contains the Al plating bath if Si content surpasses 0.3% (quality) in the steel, the obvious variation of the wellability of coating, and produce the plating leakage defective, cause degraded appearance.It is said, above-mentioned shortcoming be since in the reduced anneal process on the surface of thin steel sheet the various oxides of Si concentrate due to the various oxides and zinc wellability difference with Si.
Under the situation of high-strength steel sheet, the various elements that added explained above all resembling abundant, so the alloying heat treatment of carrying out behind the plating carries out under higher temperature usually, and time ratio mild steel is longer.This is one of obstacle that guarantees the good material quality.
In addition, consider that from the viewpoint of improving the structural member durability except corrosion resistance, fatigue resistance also is important.In other words, a kind of high-strength steel sheet with good plating production capacity, good fatigue resistance and good corrosion resistance of research and development is very important.
As a kind of measure that addresses these problems, the flat 3-28359 peace of Japanese patent application prospectus 3-64437 discloses a kind of method of improving coating performance through the extraordinary coating of plating.Yet the problem of this method is that this method need be installed a kind of new plater in the annealing furnace front of galvanizing by dipping production line, perhaps on the electroplating activity streamline, set up the plating pre-treatment, and this will improve production cost.In addition, considering fatigue resistance and corrosion resistance, is effectively although disclose interpolation copper recently, does not see the record of itself and corrosion resistance compatibility at all.
Moreover the Si scale defective that produces during hot rolling causes the coating degraded appearance in subsequent handling.It is necessary that Si content in the minimizing steel suppresses Si scale defective; But perhaps belong under the typical high ductibility type steel-sheet two-phase steel-sheet situation at the retained austenite sheet metal, Si is a kind of to improving the very effective interpolation element of balance between intensity and the ductility.In order to overcome this problem, the someone discloses the method that a kind of condition through control annealing atmosphere and so on is controlled the oxide form that produces.Yet this method requires special installation, thereby needs to increase new equipment investment.
Darker one deck; When adopting high-strength steel sheet is in order to alleviate quality and sheet metal through the reduction lamella thickness again and again during attenuate, often even need galvanizing by dipping sheet metal or galvanizing by dipping layer DIFFUSION TREATMENT sheet metal can further improve corrosion resistance.For instance, dispensing rock salt is a kind of harsh environment as the environment of snow melting agent, because rock salt contains more a large amount of Cl
-Ion.If coating is just not enough in the corrosion resistance of the part generation local shedding of the work of taking the weight or coating itself, then needs the matrix material of excellent corrosion resistance, and need to form the coating of excellent corrosion resistance.
So far also do not develop and a kind ofly allow to alleviate quality with thickness and consider the problem of intensity, relevant Si and the sheet metal that the improvement corrosion resistance is made comprehensively.
Darker one deck, when being intended to improve high-strength steel sheet plating production capacity, Japanese patent application prospectus H5-230608 discloses the galvanizing by dipping sheet metal that a kind of Al-Mn-Fe of having is a coating.Yet,, and reckon without the binding force of cladding material of high-strength high-tractility material when taking the weight work although production capacity has been considered in this patent application.
In addition, be purpose with the absorbability that improves the bump ability, Japanese patent application prospectus H11-189830 discloses a kind of sheet metal, and it has average grain size and is not more than 10 μ m, comprises ferritic principal phase; Average grain size is not more than 5 μ m, comprises 3～50% (volume) austenite or martensitic second phase of 3～30% (volumes); And can select to contain bainite.But this invention is not considered and the coating wellability, and does not provide and allow to subtract corrosion resistance thick and when following intensity to improve.
Summary of the invention
The present invention provides a kind of can solve the equal excellence of above-mentioned variety of issue, outward appearance and machinability, can improve plating leakage defective and adhesion and ductility excellent high strength zinc-plated DIFFUSION TREATMENT sheet metal and the manufacturing approach thereof of coating behind strong deformation, and the present invention also provides a kind of high-strength high-tractility galvanizing by dipping sheet metal and a kind of corrosion resistance and excellent high-strength high-tractility zinc coat DIFFUSION TREATMENT sheet metal and the manufacturing approach thereof of fatigue resistance.
In addition, the purpose of this invention is to provide a kind of high-strength hot-dip galvanized sheet metal and a kind of high-strength hot-dip galvanized layer DIFFUSION TREATMENT sheet metal and manufacturing approach thereof that can address the above problem, suppress plating leakage defective and blemish and in the environment that especially contains chlorion, have corrosion resistance and high ductibility simultaneously.
Result as various tests; All inventors of the present invention have found that, might produce a kind of even when regulating heat-treat condition, still have excellent processability, and improve the zinc coat DIFFUSION TREATMENT sheet metal of the corrosion resistance and the fatigue resistance of high-strength steel sheet simultaneously through the microscopic structure of interface between adjusting coating and basic unit's (steel layer) (below be called " coating/basic unit interface ").In addition, they also find, make coating contain an amount of element-specific, can make that the wellability of fused zinc is improved on the high-strength steel sheet.They and then discovery, the Al concentration that reduces in the coating can make above-mentioned each effect strengthen; And even under the situation of the high-strength steel sheet that contains quite a large amount of alloying elements, through Si content X% (quality), Mn content Y% (quality) and Al content Z% (quality) in the control steel and in addition the Al content A% (quality) in the coating and Mn content B% (quality) to satisfy following formula 1:
3-(X+Y/10+Z/3)-12.5×(A-B)≥0 ...1
Also can obtain very good coating.
And they also find, even through optionally adding an amount of alloying element and removing condition of heat treatment through regulating the steel-sheet microscopic structure, still can produce the sheet metal with high ductibility.
Result as various tests; All inventors of the present invention have found that; Under the situation of high-strength steel sheet; Through make coating contain an amount of element-specific and make it with sheet metal in each component combine, just can improve the wellability in the galvanizing by dipping process, quicken the alloying reaction in the alloy layer.This effect mainly realizes through Al concentration in the control coating and the Mn concentration in the steel.
They find, through Al content Z% (quality) in Mn content X% (quality) and Si content Y% (quality) and the coating in the control steel, to satisfy following formula 2:
0.6-(X/18+Y+2)≥0 ...2
Can obtain a kind of very good coating.
Result as various tests; All inventors of the present invention have found that; Under the situation of high-strength steel sheet, through make coating contain an amount of element-specific and make it with sheet metal in each composition combine, can improve the wellability in galvanizing by dipping and the galvanizing by dipping layer DIFFUSION TREATMENT process; Quicken the alloying reaction in the alloy layer, and can improve ductility and corrosion resistance.This effect can be mainly concentration through Mo in the concentration of Al and Mo in the control coating and the steel realize.
In other words, they find, make and contain 0.001% (quality) in the coating to 4% (quality) Al, and Al content A% (quality) in the control coating and the Mo content C% (quality) in Mo content B% (quality) and the steel, make it to satisfy following formula 3:
100≥(A/3+B/6)/(C/6)≥0.01 ...3
Can obtain a kind of plating sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT of high-strength high-tractility.
On the basis of above-mentioned discovery, the present invention is accomplished, and main points of the present invention are following:
(1) has the high-strength high-tractility galvanizing by dipping sheet metal and the galvanizing by dipping layer DIFFUSION TREATMENT sheet metal of high resistance fatigability and corrosion resistance; The sheet metal of this galvanizing by dipping sheet metal or galvanizing by dipping layer DIFFUSION TREATMENT has one deck coating on the substrate surface that is made up of sheet metal; It is characterized in that the depth capacity of the grain boundary oxide layer that forms at the interface between coating and basic unit is not more than 0.5 μ m.
(2) have the high-strength high-tractility galvanizing by dipping sheet metal and the galvanizing by dipping layer DIFFUSION TREATMENT sheet metal of high resistance fatigability and corrosion resistance; This galvanizing by dipping sheet metal or galvanizing by dipping layer DIFFUSION TREATMENT sheet metal have one deck coating on the substrate surface that is made up of sheet metal; It is characterized in that; The depth capacity of the grain boundary oxide layer at the interface between coating and basic unit is not more than 1 μ m, and the average grain size of principal phase is not more than 20 μ m in basic unit's microscopic structure simultaneously.
(3) above (1) or (2) described high-strength high-tractility galvanizing by dipping sheet metal and galvanizing by dipping layer DIFFUSION TREATMENT sheet metal with high resistance fatigability and corrosion resistance; This galvanizing by dipping sheet metal or galvanizing by dipping layer DIFFUSION TREATMENT sheet metal have one deck coating on the substrate surface of being made up of sheet metal; It is characterized in that the average grain size of principal phase is not more than 0.1 divided by the value of the grain boundary oxide layer depth capacity gained that forms at the interface between coating and the basic unit in basic unit's microscopic structure.
(4) (1) any one describedly has the high-strength high-tractility galvanizing by dipping sheet metal of high resistance fatigability and highly corrosion resistant and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT in (3); It is characterized in that; By volume in the sheet metal microscopic structure; Contain 50% to 97% ferrite or ferrite and bainite as principal phase, and contain a kind of in the martensite that accounts for cumulative volume 3% to 50% and the austenite or two kinds mutually as second.
(5) (1) in (4) any one described high-strength high-tractility galvanizing by dipping sheet metal and galvanizing by dipping layer DIFFUSION TREATMENT sheet metal with high resistance fatigability and corrosion resistance, it is characterized in that in mass, coating contains:
Al 0.001～0.5%, and
Mn?0.001～2％，
Surplus is zinc and unavoidable impurities; And Si content: X (quality %) in the sheet metal, Al content: A (quality %) and Mn content: B (quality %) satisfy formula 1 in Mn content: Y (quality %) and Al content: Z (quality %) and the coating:
3-(X+Y/10+Z/3)-12.5×(A-B)≥0 ...1。
The high-strength high-tractility galvanizing by dipping layer DIFFUSION TREATMENT sheet metal with high antifatigue and highly corrosion resistant described in (6) (5) is characterized in that, containing the Fe amount in the coating is 5% (quality)～20% (quality).
(7) the high-strength hot-dip galvanized sheet metal of high binding force of cladding material and ductility behind a kind of severe deformation, said galvanizing by dipping sheet metal has one deck coating, and in mass, coating contains,
Al:0.001～0.5%, and
Mn：0.001～2％，
Surplus is zinc and unavoidable impurities, and in mass, surface of thin steel sheet is made up of following compositions,
C：0.0001～0.3％，
Si：0.01～2.5％，
Mn：0.01～3％，
Al:0.001～4%, and
Surplus is iron and unavoidable impurities; It is characterized in that; Si content in the sheet metal: X (quality %), Al content: A (quality %) and Mn content: B (quality %) satisfy formula 1 in Mn content: Y (quality %) and Al content: Z (quality %) and the coating; And by volume in the sheet metal microscopic structure; Have and comprise 70% to 97% ferritic principal phase; And the average grain size of principal phase is not more than 20 μ m; And by volume, contain 3% to 30% austenite and/or martensitic second mutually and the average grain size of second phase be not more than 10 μ m:
3-(X+Y/10+Z/3)-12.5×(A-B)≥0 ...1。
The sheet metal with high-strength hot-dip galvanized layer DIFFUSION TREATMENT of high binding force of cladding material and ductility behind the severe deformation described in (8) (7) is characterized in that, also contains the Fe of 5% (quality) to 20% (quality) in the coating.
(9) (7) or (8) described in have high binding force of cladding material and the high-strength hot-dip galvanized sheet metal of ductility and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT behind the severe deformation; It is characterized in that the austenite of formation sheet metal second phase and/or martensitic average grain size are 0.01 to 0.7 times of ferrite average grain size.
(10) (7) any one describedly has binding force of cladding material and the high-strength hot-dip galvanized sheet metal of extension and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT behind the severe deformation in (9); It is characterized in that; The steel-sheet microscopic structure has the average grain size that comprises 50% (volume) to ferritic principal phase of 95% (volume) and principal phase and is not more than 20 μ m; And comprise 3% (volume) to 30% (volume) austenite and/or martensitic second mutually and the average grain size of second phase be not more than 10 μ m, also contain the bainite of 2% (volume) to 47% (volume) simultaneously.
(11) (7) any one describedly has high binding force of cladding material and the high-strength hot-dip galvanized sheet metal of ductility and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT behind the severe deformation in (10); It is characterized in that, also contain the Mo of 0.001% (quality) to 5% (quality) in the said steel.
(12) (7) any one describedly has high binding force of cladding material and the high-strength hot-dip galvanized sheet metal of ductility and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT behind the severe deformation in (11); It is characterized in that, also contain the S of the P and 0.0001% (quality) to 0.01% (quality) of 0.0001% (quality) to 0.1% (quality) in the said steel.
(13) (7) any one describedly has the high-strength hot-dip galvanized sheet metal of high antifatigue and highly corrosion resistant and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT in (12); It is characterized in that Si content is that 0.001% (quality) is to 2.5% (quality) in the steel.
(14) a kind of sheet metal with high-strength hot-dip galvanized layer DIFFUSION TREATMENT of excellent appearance and machinability, the sheet metal of said galvanizing by dipping layer DIFFUSION TREATMENT has one deck coating, and in mass, this coating contains,
Mn：0.001％～3％，
Al：0.001％～4％，
Mo:0.0001%～1%, and
Fe：5％～20％，
Surplus is zinc and unavoidable impurities, in mass, contains on the surface of thin steel sheet
C：0.0001％～0.3％
Si:0.001%～be lower than 0.1%
Mn：0.01％～3％
Al：0.001％～4％
Mo：0.001％～1％
P：0.0001％～0.3％
S:0.0001%～0.1% and
Surplus is iron and unavoidable impurities, it is characterized in that the Mn content in the steel: X (quality %) and Si content: Y (quality %) satisfy formula 2 with the Al content in the coating: Z (quality %):
0.6-(X/18+Y+Z)≥0 ...2。
(15) a kind of high-strength hot-dip galvanized sheet metal with excellent appearance and machinability, said galvanizing by dipping sheet metal has one deck coating, and in mass, this coating contains,
Mn?0.001％～3％，
Al?0.001％～4％，
Mo 0.0001%～1%, and
Fe is less than 5%,
Surplus is zinc and unavoidable impurities, in mass, contains on the surface of thin steel sheet
C：0.0001％～0.3％，
Si:0.001% is to less than 0.1%,
Mn：0.01％～3％，
Al：0.001％～4％，
Mo：0.001％～1％，
P：0.0001％～0.3％，
S:0.0001%～0.1%, and
Surplus is Fe and unavoidable impurities, it is characterized in that, the Al content in the Mn content in the steel: X (quality %) and Si content: Y (quality %) and the coating: Z (quality %) satisfies formula 2:
0.6-(X/18+Y+Z)≥0 2。
(16) a kind of sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT of the high-strength high-tractility with highly corrosion resistant, the sheet metal of said galvanizing by dipping layer DIFFUSION TREATMENT has one deck coating, and in mass, this coating contains,
Al 0.001～4%, and
Fe?5％～20％，
Surplus is zinc and unavoidable impurities, in mass, contains on the surface of thin steel sheet
C：0.0001～0.3％，
Si:0.001～less than 0.1%,
Mn：0.001～3％，
Al：0.001～4％，
Mo：0.001～1％，
P：0.001～0.3％，
S:0.0001～0.1%, and
Surplus is Fe and unavoidable impurities, it is characterized in that, in the coating in Al content A (quality %) and Mo content B (quality %) and the steel Mo content C (quality %) satisfy formula 3; And the microscopic structure of steel comprises that by accounting for 3% to 50% (volume) that 50% to 97% (volume) comprise principal phase and the surplus of ferrite or ferrite and bainite the complex tissue of martensite or martensite and retained austenite forms:
100≥(A/3+B/6)/(C/6)≥0.01 3。
(17) a kind of galvanizing by dipping sheet metal with high-strength high-tractility of highly corrosion resistant, said galvanizing by dipping sheet metal has one deck coating, and in mass, this coating contains,
Al:0.001～4%, and
Fe: be lower than 5%,
Surplus is zinc and unavoidable impurities, in mass, contains on the surface of thin steel sheet
C：0.0001～0.3％，
Si:0.001～be lower than 0.1%,
Mn：0.001～3％，
Al：0.001～4％，
Mo：0.001～1％，
P：0.001～0.3％，
S:0.0001～0.1%, and
Surplus is Fe and unavoidable impurities, it is characterized in that, in the coating in Al content A (quality %) and Mo content B (quality %) and the steel Mo content C (quality %) satisfy formula 3; And the microscopic structure of steel comprises that by 50% to 97% (volume) 3% to 50% (volume) of principal phase and the surplus of ferrite or ferrite and bainite comprises that the complex tissue of martensite or martensite and retained austenite forms:
100≥(A/3+B/6)/(C/6)≥0.01 ...3。
(18) (14) any one describedly has the high-strength hot-dip galvanized sheet metal of excellent appearance and machinability and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT in (17); It is characterized in that the microscopic structure of steel comprises that by 50% to 97% (volume) 3% to 50% (cumulative volume) of principal phase and the surplus of ferrite or ferrite and bainite comprises that the complex tissue of martensite or martensite and retained austenite forms.
(19) (14) any one describedly has the high-strength hot-dip galvanized sheet metal of excellent appearance and machinability and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT in (18); It is characterized in that; The microscopic structure of steel has the average grain size that comprises 70% (volume) to ferritic principal phase of 97% (volume) and principal phase and is not more than 20 μ m, and comprise 3% (volume) to 30% (volume) austenite and/or martensitic second mutually and the average grain size of second phase be not more than 10 μ m.
(20) (14) any one describedly has the high-strength hot-dip galvanized sheet metal of excellent appearance and machinability and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT in (19), it is characterized in that, steel-sheet second is made up of austenite; And C content C (quality %) and Mn content Mn (quality %) and austenitic percent by volume V in the steel
γThe percent by volume V of (with %) and ferrite and bainite
α(with %) satisfies formula 4:
(V
γ+V
α)/V
γ×C+Mn/8≥2.0 ...4。
(21) (14) any one describedly has the high-strength hot-dip galvanized sheet metal of excellent appearance and machinability and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT in (20); It is characterized in that; The steel-sheet microscopic structure has the average grain size that comprises 50% (volume) to ferritic principal phase of 95% (volume) and principal phase and is not more than 20 μ m; And comprise 3% (volume) to 30% (volume) austenite and/or martensitic second mutually and the average grain size of second phase be not more than 10 μ m, also contain the bainite of 2% (volume) to 47% (volume) simultaneously.
(22) (14) any one describedly has the high-strength hot-dip galvanized sheet metal of highly corrosion resistant and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT in (21); It is characterized in that the austenite of formation sheet metal second phase and/or martensitic average grain size are 0.01 to 0.6 times of ferrite average grain size.
(23) (1) in (22) any one described high-strength hot-dip galvanized sheet metal with high binding force of cladding material and ductility behind the severe deformation, it is characterized in that in mass, coating also contains:
Ca：0.001～0.1％，
Mg：0.001～3％，
Si：0.001～0.1％，
Mo：0.001～0.1％，
W：0.001～0.1％，
Zr：0.001～0.1％，
Cs：0.001～0.1％，
Rb：0.001～0.1％，
K：0.001～0.1％，
Ag：0.001～5％，
Na：0.001～0.05％，
Cd：0.001～3％，
Cu：0.001～3％，
Ni：0.001～0.5％，
Co：0.001～1％，
La：0.001～0.1％，
Tl：0.001～8％，
Nd：0.001～0.1％，
Y：0.001～0.1％，
In：0.001～5％，
Be：0.001～0.1％，
Cr：0.001～0.05％，
Pb：0.001～1％，
Hf：0.001～0.1％，
Tc：0.001～0.1％，
Ti：0.001～0.1％，
Ge：0.001～5％，
Ta：0.001～0.1％，
V:0.001～0.2%, and
B：0.001～0.1％
In one or more.
(24) (1) any one describedly has the high-strength hot-dip galvanized sheet metal of excellent appearance and machinability and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT in (23), it is characterized in that, in mass, also contain in the steel,
Cr：0.001～25％，
Ni：0.001～10％，
Cu：0.001～5％，
Co:0.001～5%, and
W：0.001～5％
In one or more.
(25) (1) any one describedly has sheet metal excellent appearance and machinability, high-strength hot-dip galvanized sheet metal and galvanizing by dipping layer DIFFUSION TREATMENT in (24); It is characterized in that; In mass, also containing total amount in the steel is among 0.001 to 1% Nb, Ti, V, Zr, Hf and the Ta one or more.
(26) (1) any one describedly has the high-strength hot-dip galvanized sheet metal of excellent appearance and machinability and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT in (25); It is characterized in that; In mass, also containing total amount in the steel is 0.0001 to 0.1% B.
(27) (1) any one describedly has the high-strength hot-dip galvanized sheet metal of excellent appearance and machinability and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT in (26); It is characterized in that; In mass, also contain among 0.0001 to 1% Y, Rem, Ca, Mg and the Ce one or more in the steel.
(28) (1) in (27) any one described sheet metal with high strength, high ductibility galvanizing by dipping sheet metal and galvanizing by dipping layer DIFFUSION TREATMENT of high antifatigue and highly corrosion resistant; It is characterized in that; In area percentage; In scope, contain total amount in the steel and be 0.1 to 70% SiO from the interface between coating and the sheet metal to the 10 μ m degree of depth
2, MnO and Al
2O
3In one or more; And satisfy formula 5:
{ MnO (% (area))+Al
2O
3(% (area)) }/SiO
2(% (area))>=0.1 ... 5.
(29) (1) any one describedly has the high-strength high-tractility galvanizing by dipping sheet metal of high antifatigue and highly corrosion resistant and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT in (28); It is characterized in that; In area percentage; From the interface between coating and the sheet metal in 10 μ m depth boundses, contain total amount in the steel and be 0.0001 to 10.0% Y
2O
3, ZrO
2, HfO
2, TiO
3, La
2O
3, Ce
2O
3, CeO
2, among CaO and the MgO one or more.
(30) a kind of be used to prepare have high binding force of cladding material and the high-strength hot-dip galvanized sheet metal of ductility and the steel-sheet method of galvanizing by dipping layer DIFFUSION TREATMENT behind the severe deformation; It is characterized in that; To comprise (1) the steel casting of any one said chemical composition in (29), perhaps after casting, cool off bloom slab once; And then heat above-mentioned bloom slab; Then bloom slab is rolled into hot rolled steel sheet and it is batched, then pickling and cold rolling above-mentioned hot rolled steel sheet; Then, be not less than 0.1 * (Ac
3-Ac
1)+Ac
1(℃) to not being higher than Ac
3+ 50 (℃) temperature range in, with above-mentioned cold-reduced sheet annealing 10 seconds to 30 minutes; Then with the cooldown rate of 0.1～10 ℃/sec, above-mentioned sheet metal is cooled to 650 to 700 ℃ temperature range; Then, with the cooldown rate of 1～100 ℃/sec, above-mentioned sheet metal is cooled in the temperature range of bath temperature to bath temperature+100 ℃; Sheet metal is remained in the temperature range of zinc bath temperature to zinc bath temperature+100 ℃ and reach 1 to 3000 second, the above-mentioned time comprises dip time subsequently; Sheet metal is immersed in the zinc plating bath; Afterwards, above-mentioned sheet metal is cooled to room temperature.
(31) a kind ofly be used for preparing (1) steel-sheet method to (29) any one described high-strength hot-dip galvanized sheet metal and galvanizing by dipping layer DIFFUSION TREATMENT; Said galvanizing by dipping sheet metal has fabulous outward appearance and machinability; It is characterized in that; To comprise steel casting, perhaps after casting, cool off bloom slab once like any one said chemical composition in (1) to (29); And then heat above-mentioned bloom slab and reach 1180 to 1250 ℃; Accomplish hot rolling 880 to 1100 ℃ temperature; Pickling and the cold rolling above-mentioned hot rolled steel sheet that batches then; Then, be not less than 0.1 * (Ac
3-Ac
1)+Ac
1(℃) to not being higher than Ac
3+ 50 (℃) temperature range in, with above-mentioned cold-reduced sheet annealing 10 seconds to 30 minutes; Then with the cooldown rate of 0.1～10 ℃/sec, above-mentioned sheet metal is cooled to 650 to 700 ℃ temperature range; Then, with the cooldown rate of 0.1～100 ℃/sec, above-mentioned sheet metal is cooled in the temperature range of bath temperature-50 ℃ to bath temperature+50 ℃; Then sheet metal is immersed in the plating bath; Sheet metal is remained in the temperature range of bath temperature-50 ℃ to bath temperature+50 ℃ and reach 2 to 200 seconds, the above-mentioned time comprises dip time; Afterwards, above-mentioned sheet metal is cooled to room temperature.
(32) a kind ofly be used for preparing (1) steel-sheet method to (29) any one described high-strength high-tractility galvanizing by dipping sheet metal and galvanizing by dipping layer DIFFUSION TREATMENT; Said galvanizing by dipping sheet metal has fabulous corrosion resistance; It is characterized in that; To comprise steel casting, perhaps after casting, cool off bloom slab once like any one said chemical composition in (1) to (29); And then heat above-mentioned bloom slab and reach 1200 to 1300 ℃; Then with total reduction ratio of 60 to 99%, under 1000 to 1150 ℃ temperature, the heated bloom slab of roughing; Pickling and cold rolling above-mentioned fine finishining and the hot rolled steel sheet that batches then; Then, be not less than 0.12 * (Ac
3-Ac
1)+Ac
1(℃) to not being higher than Ac
3+ 50 (℃) temperature range in, with above-mentioned cold-reduced sheet annealing 10 seconds to 30 minutes; Then, after the annealing, the highest annealing temperature in the time will annealing be defined as Tmax (℃) time, with the cooldown rate of Tmax/1000-Tmax/10 ℃/sec, above-mentioned sheet metal is cooled to Tmax-200 ℃ to Tmax-100 ℃ temperature range; Then, with the cooldown rate of 0.1～100 ℃/sec, above-mentioned sheet metal is cooled in the temperature range of bath temperature-30 ℃ to bath temperature+50 ℃; Then sheet metal is immersed in the plating bath; Sheet metal is remained in the temperature range of bath temperature-30 ℃ to bath temperature+50 ℃ and reach 2 to 200 seconds, the above-mentioned time comprises dip time; Afterwards, above-mentioned sheet metal is cooled to room temperature.
(33) a kind of steel-sheet method that is used to prepare high-strength high-tractility galvanizing by dipping sheet metal galvanizing by dipping layer DIFFUSION TREATMENT with high antifatigue and highly corrosion resistant; It is characterized in that; To comprise (1) the steel casting of any one said chemical composition in (29), perhaps after casting, cool off bloom slab once; And then heat above-mentioned bloom slab; Then bloom slab is rolled into hot rolled steel sheet and it is batched, then pickling and cold rolling above-mentioned hot rolled steel sheet; Maximum temperature when then, the control annealing temperature makes annealing can drop on and be not less than 0.1 * (Ac
3-Ac
1)+Ac
1(℃) to not being higher than Ac
3-30 (℃) temperature range in the annealing of above-mentioned cold-reduced sheet; Then with the cooldown rate of 0.1～10 ℃/sec, above-mentioned sheet metal is cooled to 650 to 710 ℃ temperature range; Then, with the cooldown rate of 1～100 ℃/sec, above-mentioned sheet metal is cooled in the temperature range of zinc bath temperature to zinc bath temperature+100 ℃; Sheet metal is remained in the temperature range of zinc bath temperature to zinc bath temperature+100 ℃ and reach 1 to 3000 second, the above-mentioned time comprises dip time subsequently; Sheet metal is immersed in the zinc plating bath; Afterwards, cool off above-mentioned sheet metal to room temperature.
(34) a kind of have high binding force of cladding material and the high strength hot dipping zinc plating sheet metal of ductility and a sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT behind high antifatigue, highly corrosion resistant, the severe deformation; And (30) in (33) any one described be used to prepare have high binding force of cladding material and the high-strength hot-dip galvanized sheet metal of ductility and the steel-sheet method of galvanizing by dipping layer DIFFUSION TREATMENT behind high antifatigue, highly corrosion resistant, the severe deformation; It is characterized in that; After sheet metal being immersed in the zinc plating bath; Carry out Alloying Treatment at 300 to 550 ℃, then sheet metal is cooled to room temperature.
Realize best mode of the present invention
To specify the present invention below.
Embodiment 1
The inventor is in mass a kind of, the C by 0.0001～0.3%, and 0.001～2.5% Si, 0.01～3% Mn, the sheet metal that 0.001～4% the Al and the iron of surplus and unavoidable impurities are formed is handled: be not less than 0.1 * (Ac
3-Ac
1)+Ac
1(℃) to not being higher than Ac
3+ 50 (℃) temperature range in, with above-mentioned cold-reduced sheet annealing annealing in 10 seconds to 30 minutes; Then with the cooldown rate of 0.1～10 ℃/sec, above-mentioned sheet metal is cooled to 650 to 700 ℃ temperature range; Then, with the cooldown rate of 1～100 ℃/sec, above-mentioned sheet metal is cooled in the temperature range of bath temperature (450 to 470 ℃) to bath temperature+100 ℃; Sheet metal was flooded for 3 seconds in 450 to 470 ℃ of zinc plating baths; 500 to 550 ℃ of heating 10 to 60 seconds of sheet metal.
Then, assess plating performance through measuring by the area of plating leakage part on the plating surface of thin steel sheet.Through salt spray test assessment corrosion resistance repeatedly.Carry out plain bending fatigue test assessment by plating steel-sheet fatigue behaviour also through tension test assessment mechanical performance, and through the pressure that applies corresponding to sheet metal tensile strength 50%.
Further, after applying 20% stretcher strain, through sheet metal is applied 60 ° of bendings and backward bending forming assess binding force of cladding material.The polyethylene band is sticked on the part of carrying out behind the bending forming and it is peeled off, measure the area that coating is stripped from through graphical analysis then.
The result; Especially, observe a large amount of Si system oxides on the grain boundary at the interface between coating and the basic unit, and; The inventor finds; Relation between the form of considering the grain boundary oxide layer and fatigue behaviour, through the depth capacity of control grain boundary oxide layer and in the final microscopic structure that obtains the average particle size particle size of principal phase, can prepare a kind of galvanizing by dipping sheet metal fabulous fatigue resistance and corrosion resistance, high strength, high ductibility that has.
That is, the inventor finds, contains the depth capacity of the grain boundary oxide layer of 0.5 μ m or littler Si on the crystal boundary between coating and the basic unit through being controlled at, the final microscopic structure that obtains, and can prolong galvanizing by dipping steel-sheet fatigue life.In addition, through selecting the composition and the preparation condition of steel, can prolong galvanizing by dipping steel-sheet fatigue life further.It is 0.5 μ m or littler that said preparation condition allows the depth capacity of grain boundary oxide layer, better is 0.2 μ m or littler.
In addition; The inventor finds; Kind and area percentage through oxide in the restriction steel can improve corrosion resistance and fatigue resistance further after alloying is handled, contain grain boundary oxide at the depth bounds from the interface between coating and sheet metal to 10 μ m in the steel.That is, a kind of sheet metal with high strength, high ductibility galvanizing by dipping sheet metal or galvanizing by dipping layer DIFFUSION TREATMENT of excellent corrosion resistance, fatigue resistance can obtain through following manner: as oxide, make and contain SiO in the steel
2, MnO and Al
2O
3In one or more, it occupies 0.4 to 70% of gross area percentage in the depth bounds from the interface between coating and the sheet metal to 10 μ m, and controls above-mentioned area percentage and make it to satisfy expression:
{ MnO (% (area)) Al
2O
3(% (area)) }/SiO
2(% (area))>=0.1.
The inventor also finds, through removing SiO
2, MnO and Al
2O
3Outside, with 0.0001 to 10.0% of gross area percentage, Xiang Gangzhong adds Y in the depth bounds from the interface between coating and the sheet metal to 10 μ m
2O
3, ZrO
2, HfO
2, TiO
2, La
2O
3, Ce
2O
3, CeO
2, among CaO and the MgO one or more, also can after Alloying Treatment, improve corrosion resistance and fatigue resistance.
The measurement that as stated, is present in evaluation, observation and the area percentage of the oxide the steel in the depth bounds of 10 μ m at the interface between coating and sheet metal here, can be carried out through using EPMA, FE-SEM and similar approach.Among the present invention, under 2000 to 20000 magnifying power,, use the analysis data of graphical analysis to obtain area percentage then through measuring area more than 50 visual fields.The reproduction copies that extracts through preparation also uses TEM or EBSP identifies oxide.Distinguish above-mentioned MnO, Al through using the most similar object of elementary analysis and structure evaluation discovery
2O
3And SiO
2Although having object sometimes is the situation that contains the composite oxides of other atom or have the structure of a lot of defectives.Area scanning through using EPMA, FE-SEM and similar approach to carry out each composition obtains area percentage.In this case, be difficult although accurately identify each structure, but still can judge together through form, tissue and said structure analysis.Then, can be through the data that obtained by area scanning be carried out the percentage that graphical analysis obtains each area.
The inventor finds, is not more than in 20 μ m and the microscopic structure through the average particle size particle size of controlling principal phase in the sheet metal, and the depth capacity of the grain boundary oxide layer on interface between coating and the basic unit is not more than 1 μ m can prolong fatigue life equally.In addition; They find; Come the value that obtains except that the depth capacity that is formed on the grain boundary oxide layer on the interface between coating and the basic unit through control with principal phase average particle size particle size in the sheet metal microscopic structure, can obtain a kind of sheet metal with high strength, high ductibility galvanizing by dipping sheet metal and galvanizing by dipping layer DIFFUSION TREATMENT of excellent fatigue resistance and corrosion resistance.
In addition; About plating performance and corrosion resistance, have found that, as long as Si content: X (quality %) in the sheet metal; Al content: A (quality %) and Mn content: B (quality %) satisfy formula 1 in Mn content: Y (quality %) and Al content: Z (quality %) and the coating; Even when in sheet metal, containing a large amount of especially Si, also can not form the plating leakage defective, and the formation of in salt spray test repeatedly, becoming rusty is also considerably less:
3-(X+Y/10+Z/3)-12.5×(A-B)≥0 ...1。
Formula 1 is to show when composition in sheet metal and the coating is to the wetting sex data of plating newfound through multiple regression analysis.
Here, coating is confirmed the composition in the coating through the chemical analysis measured value after being contained dissolving with hydrochloric acid corrosion inhibiter, 5%.
Embodiment 2
The inventor is in mass a kind of, by
C：0.0001～0.3％，
Si:0.001～be lower than 0.1%,
Mn：0.01～3％，
Al：0.001～4％，
Mo：0.001～1％，
P：0.0001～0.3％，
S：0.0001～0.1％，
And the sheet metal of the iron of surplus and unavoidable impurities composition is handled as follows: with above-mentioned sheet metal annealing; Sheet metal was flooded for 3 seconds in 450 to 470 ℃ zinc plating bath; And then at 500 to 530 ℃ with 10 to 60 seconds of sample segment heating.Then, the defective that occurs on the surface of thin steel sheet with plating is divided into 5 grades and assesses the surface.Mechanical performance is assessed with tension test.The result finds, Mn content is defined as X (quality %) and Si content is Y (quality %) in steel, and Al content is Z (quality %) and X, Y and Z when satisfying formula 2 in the coating:
0.6-(X/18+Y+Z)≥0 ...2
Can evaluation grade 5, it is a kind of grade that does not almost observe blemish that means.
Can assess by plating steel-sheet surface through the state of visual observation plating leakage defective formation and the formation state of flaw and decorative pattern (patterns), and they are divided into 1 to 5 evaluation grade.Evaluation criteria is following:
Evaluation grade 5: almost do not observe plating leakage defective, flaw and decorative pattern (area percentage no more than 1%),
Evaluation grade 4: plating leakage defective, flaw and the decorative pattern (area percentage is more than 1% to no more than 10%) of trace are arranged,
Evaluation grade 3: a spot of plating leakage defective, flaw and decorative pattern (area percentage is more than 10% to no more than 50%) are arranged,
Evaluation grade 2: a large amount of plating leakage defective, flaw and decorative pattern (area percentage is more than 50%) are arranged,
Evaluation grade 1: plating can not wetting surface of thin steel sheet.
Embodiment 3
The inventor is in mass a kind of, by
C：0.0001～0.3％，
Si:0.001～be lower than 0.1%,
Mn：0.01～3％，
Al：0.001～4％，
Mo：0.001～1％，
P：0.0001～0.3％，
S：0.0001～0.1％，
And the sheet metal of the iron of surplus and unavoidable impurities composition is handled as follows: with above-mentioned sheet metal annealing; Sheet metal was flooded for 3 seconds in 450 to 470 ℃ zinc plating bath; And then, sample segment was heated for 10 to 60 seconds at 500 to 550 ℃.Then, sheet metal is carried out sufficient flat wise bend (R=1t); Then, based on the Society of Automotive Engineers of Japan, Inc.(JASE) standard (JASO) is carried out the cyclic corrosion test up to 150 circulations with crooked sample.Through using light microscope, the magnifying power 200 to 1000 is observed the appearance that is no less than 20 visual fields and section outward appearance with the evaluation of corrosion state; Observe the degree that the corrosion development gets into the inside, and observed result is divided into 5 grades.Evaluation criteria is following:
Evaluation grade 5: the corrosion development degree: only the corrosion depth of corrosion of coating or base material is lower than 50 μ m,
Evaluation grade 4: corrosion development degree: the corrosion depth of base material is 50 μ m to being lower than 100 μ m,
Evaluation grade 3: corrosion development degree: the corrosion depth of base material is lower than the half the of sheet metal thickness,
Evaluation grade 2: corrosion development degree: the corrosion depth of base material is not less than the half the of sheet metal thickness,
Evaluation grade 1: perforation.
The result; Find that in coating Al content is in 0.001 to 4% scope and be defined as A (quality %); Mo content is defined as B (quality %) in the coating; Mo content is defined as C (quality %) in the steel, and A, B and C can obtain the good evaluation grade of corrosion resistance 4 or 5 when satisfying formula 3:
100≥(A/3+B/6)/(C/6)≥0.01 ...3
Why repressed detailed reason may not be clearly to the plating leakage defective entirely, but estimates to produce the plating leakage defective
Reason is owing to add Al that advances in the plating bath and the SiO that is formed on surface of thin steel sheet
2Between the cause of wettable difference.So, add the unit of advancing the Al adverse effect in the zinc plating bath usually to suppress the plating leakage generation of defects be possible through adding to remove.As the result that the inventor conscientiously studies, find to achieve the above object through the Mn that adds the debita spissitudo scope.Estimate Mn and preferentially form oxide-film and therefore strengthened it with the reactivity that is formed on the Si system oxide-film on the surface of thin steel sheet than adding the Al that advances in the zinc plating bath.
In addition, according to estimates, Si content suppresses the Si squama by the caused flaw generation that forms during the hot rolling in the steel through reducing, and also is effective to improving outward appearance.In addition, consider that the minimizing of following Si content can cause the reduction of quality of materials, find to obtain ductility, find simultaneously that when quickening alloying reducing Si content is effective with adding Al through regulating preparation condition and adding other composition for example Al and Mo.
Though reason and unclear estimates it is because different (electromotive force is different) of the form of plating leakage generation of defects, other defective and base material and corrosion resistance of coating cause in detail.
Here, although the deposition of plating does not have special regulation, from corrosion proof angle, preferably the deposition on a side surface is no less than 5g/mm
2Although the coating of a kind of upper strata is used for galvanizing by dipping sheet metal of the present invention in order to improve paintability and wettable performance; And with multiple processing for example chromaking is handled, phosphatization is handled, lubricity improve handle, weldability improves to handle or the like and is used for galvanizing by dipping sheet metal of the present invention, but these measures do not depart from the present invention.
The preferred microscopic structure of base steel sheet
The preferred microscopic structure of base steel sheet then, is described below.In order fully to obtain ductility, preferably make principal phase be organized as ferritic phase.Yet; When the higher intensity of needs, can contain the bainite phase, but from obtaining the angle of ductility; The expectation principal phase contains by volume; Be not less than 50%, compound (term " ferrite or ferrite and bainite " except that special instruction is arranged, the same) mutually of preferred 70% ferritic single phase or ferrite and bainite with the meaning of describing in the specification.Under the compound situation mutually that is ferrite and bainite, in order to obtain reliable ductility, the ferrite by volume that expectation contains is not less than 50%.On the other hand, in order to guarantee high strength and high ductibility, ferrite that preferably contains or ferrite and bainite by volume, no more than 97% with good balance mode.In addition, in order to guarantee high strength and high ductibility simultaneously, desirable tissue is for containing retained austenite and/or martensitic complex tissue.In order to guarantee high strength and high ductibility simultaneously, preferably contain by volume, be no less than 3% retained austenite and/or martensite.But if total value surpasses 50%, then sheet metal is easy crisp, so the above-mentioned value by volume of expectation control is no more than 30%.
In order to guarantee the high ductibility of sheet metal self, stipulate that austenite and/or martensitic average particle size particle size that ferritic average particle size particle size is not more than 20 μ m and forms second phase are not more than 10 μ m.Here, expectation second is made up of austenite and/or martensite, and makes austenite and/or martensitic average particle size particle size be not more than 0.7 times of ferritic average particle size particle size of composition principal phase.But, owing in actual fabrication process, be difficult to make the austenite of forming second phase and/or martensitic average particle size particle size 0.01 times less than ferritic average particle size particle size, so preferred ratio is for being not less than 0.01.
In addition; For guarantee good binding force of cladding material and well balance guarantee high strength and high ductibility; Under the situation that sheet metal second is made up of austenite, C content: C (quality %) and Mn content: Mn (quality %) and austenitic percent by volume: V in the regulation steel
γThe percent by volume of (with %) and ferrite and bainite: V
α(with %) satisfies formula 4:
(V
γ+V
α)/V
γ×C+Mn/8≥2.0 ...4
Through satisfying above-mentioned expression formula, can obtain the sheet metal that intensity and ductility are all fabulous, have good binding force of cladding material.
Explained later is in the percent by volume and the similar content that contain under the situation of bainite.In order to improve intensity, by volume, containing and being no less than 2% bainite is effectively mutually, and, when it exists with austenite mutually jointly, help stable austenite, as a result of, help to guarantee high n value.In addition, above-mentioned phase constitution is tiny basically, therefore between strong operational period, also can help the adhesiveness of coating.Especially, under second situation about being made up of austenite, the percent by volume through the control bainite is not less than 2%, and applying adhesiveness and ductility can further improve evenly.On the other hand, because ductility is worsened,, the percent by volume of bainite phase is not higher than 47% so being restricted to.
Except foregoing, be used for sheet metal of the present invention and comprise that those contain by volume and are not higher than one or more the sheet metal in 1% the carbide as the microstructure nubbin, nitride, sulfide and the oxide.Here; Through use potassium nitrate reagent or in unexamined Japanese patent application prospectus S59-219473 disclosed reagent in rolling direction or cross-directional etching steel-sheet cross section; Can carry out the percent by volume of remnant tissue in observation, average particle size particle size (particle size of average circle of equal value) and ferrite, bainite, austenite, each phase, interface oxide layer thing and the microscopic structure in the martensite of quantitative detection evaluation, position, and under 500 to 1000 magnifying power, observe horizontal interface through light microscope.
Sometimes have the situation that almost can not measure the martensite particle size through light microscope here.Under the sort of situation, can pass through to observe the border of martensitic whole block (blocks), splicing object (packets) or aggregation (aggregates), and obtain average round particle size of equal value with sweep electron microscope measurement particle size.
In addition; Use sweep electron microscope and transmission electron microscope at the interface the form of grain boundary oxide layer between coating and the basic unit is observed and to identify; Through observing the degree of depth that is no less than 20 visibility regions under 1000 the magnifying power and measure depth capacity being not less than, and confirm its maximum.
Average particle size particle size be defined as so that use said method, through being the basis being no less than the result that 20 visibility region objects of observation obtain, the value that obtains through regulated procedure among the JIS
Then, coating will be described below.
In mass, preferably Al content in the coating is controlled at 0.001 to 0.5% scope.This be because, in mass, when Al content is lower than 0.001%; Significantly form dregs and therefore can not obtain good surface appearance, and, in mass; When the Al that adds surpasses 0.5%, significantly suppressed alloying reaction and therefore formed hot dipping alloy zinc coat hardly.
In mass, why Mn content is set at the reason of 0.001 to 2% scope and is in the coating, in this scope, does not produce the plating leakage defective and can obtain the coating of good appearance.In mass, when Mn content surpassed 2%, the Mn-Zn compound deposited in plating bath and gets into coating, causes outward appearance significantly to worsen.
In addition, have under the situation of spot weldability and coating, can improve above-mentioned performance through using Alloying Treatment in special expectation.Especially, after sheet metal is submerged in the zinc plating bath, under 300 to 550 ℃,, can makes Fe get into coating, thereby obtain a kind of high-strength hot-dip galvanized sheet metal with fabulous paintability and spot welding characteristics through using Alloying Treatment.After Alloying Treatment, in mass, Fe content is lower than at 5% o'clock, and spot welding characteristics is good inadequately.On the other hand, in mass, when Fe content surpassed 20%, therefore the adhesion of coating self worsens also made coating destruction, peel off and cling mould during operation, during forming, cause the crack.So when using Alloying Treatment, in mass, the Fe content in the coating is set at 5 to 20%.
In addition, find to suppress the plating leakage defective through in coating, containing among Ca, Mg, Si, Mo, W, Zr, Cs, Rb, K, Ag, Na, Cd, Cu, Ni, Co, La, Tl, Nd, Y, In, Be, Cr, Pb, Hf, Tc, Ti, Ge, Ta, V and the B one or more.
Although the coating deposition amount is not stipulated especially, consider that from corrosion proof angle preferably the deposition at a side surface is not less than 5g/mm here,
2Although in order to improve paintability and solderability; In galvanizing by dipping sheet metal of the present invention, use a kind of upper strata plating; For example chromaking is handled, phosphatization is handled, lubricity improves processing, the weldability raising is handled or the like but in galvanizing by dipping sheet metal of the present invention, can use multiple processing, and these situation do not depart from the present invention.
As a kind of impurity in the coating, Mn is an example.When Mn content in the coating increases to the conventional levels above impurity, produce the plating leakage defective hardly.Yet, since the restriction of relevant electroplating device, the very difficult content that increases Mn in the coating.So the present invention allows Mn content in mass, is not less than 0.001%; Above-mentioned content is in the level of impurity element, and this point is an invention, wherein; Even, also can obtain the sheet metal of minimum plating leakage defective and blemish not being to have a mind when adding Mn in the plating bath.
Stipulate following column element in mass, in said scope: Ca:0.001～0.1%, Mg:0.001～3%, Si:0.001～0.1%, Mo:0.001～0.1%; W:0.001～0.1%, Zr:0.001～0.1%, Cs:0.001～0.1%, Rb:0.001～0.1%, K:0.001～0.1%; Ag:0.001～5%, Na:0.001～0.05%, Cd:0.001～3%, Cu:0.001～3%, Ni:0.001～0.5%; Co:0.001～1%, La:0.001～0.1%, Tl:0.001～8%, Nd:0.001～0.1%, Y:0.001～0.1%; In:0.001～5%, Be:0.001～0.1%, Cr:0.001～0.05%, Pb:0.001～1%; Hf:0.001～0.1%, Tc:0.001～0.1%, Ti:0.001～0.1%, Ge:0.001～5%; Ta:0.001～0.1%, V:0.001～0.2% and B:0.001～0.1%, its reason is: in each scope, the plating leakage defective is suppressed and obtains to have the coating of good appearance.Prescribe a time limit when each element surpasses on each, form the dregs that contain each element, thereby the plating outward appearance worsens significantly.
Then, the reason of composition range in the interpretation steel of the present invention below.
For the balance of proof strength and ductility well, need to guarantee the percent by volume of second phase, be exactly for abundant assurance percent by volume and add the C element.Especially, when second was made up of austenite mutually, C not only helped to guarantee the acquisition of percent by volume, and therefore helped stability and a large amount of ductility that improve.For the proof strength and second mutually the percent by volume, in mass, lower limit is set to 0.0001%.In order to keep solderability, in mass, the upper limit is set to 0.3%.
Adding the Si element is to be used to form the ferritic formation of principal phase and the formation that inhibition can cause the carbide that balance worsens between intensity and the ductility in order to promote, in mass, lower limit is set to 0.01%.On the other hand, its excessive interpolation can cause adverse effect to weldability and plating wettability again.In addition, because C promotes the formation of inner grain boundary oxide layer, so C must be suppressed in reduced levels.So in mass, the upper limit is set to 2.5%.Especially, when being outward appearance, for example scale defective or analog become problem, rather than intensity confirms that in mass C is reduced to 0.001% when becoming problem, and this numerical value is not positioned at can cause the operational issue scope.
The purpose of adding Mn is not only in order to control plating wettable and plating adhesion, and is in order to improve intensity.In addition, add it also for the deposition that suppresses carbide with can cause intensity and pearlitic formation that ductility worsens.For this reason, Mn content is set to and is not less than 0.001% in mass.On the other hand, since when second is made up of austenite, Mn can postpone to help the conversion of bainite, and this conversion is favourable to ductility, but unfavorable to solderability, so in mass, the upper limit of Mn is set to 3%.
Al can control plating wetability and binding force of cladding material and especially effectively, when second is made up of austenite, can promote to help to improve the transformation of the bainite of ductility, and Al can also improve the balance between intensity and the ductility.In addition, Al also is a kind of element that can suppress the inner grain boundary oxide formation of Si system effectively.So the addition of Al is set in mass, is not less than 0.0001%.On the other hand, because its excessive interpolation can significantly worsen solderability and plating wettability again and therefore significantly suppress synthetic reaction, therefore, in mass, its upper limit is set to 4%.
Adding Mo is in order to suppress carbide and the pearlitic formation that can cause intensity and ductility to worsen.Under the heat-treat condition that relaxes, Mo is the important element of well balanced between proof strength and ductility.So in mass, the lower limit of Mo is set to 0.001%.In addition, owing to its excessive interpolation produces retained austenite, reduces stability and makes the ferrite hardening cause ductility to worsen, so its upper limit is set to 5%, is preferably 1%.
Add Mg, Ca, Ti, Y, Ce and Rem and be in order to suppress to cause the generation of the inner grain boundary oxide layer of Si system that plating wettable, fatigue resistance and corrosion resistance worsen.Because these elements do not produce grain boundary oxide such as Si is an oxide, but can produce quite tiny oxide by dispersing mode, the oxide of above-mentioned element self does not have adverse effect to fatigue resistance.In addition, because these elements have suppressed the generation of the inner grain boundary oxide layer of Si system, so the degree of depth of inner grain boundary oxide layer can reduce, therefore above-mentioned element helps to prolong fatigue life.Can add in the above-mentioned element one or more, the addition of these elements is set to and is not less than 0.0001% in gross mass.On the other hand, because the manufacturability that their excessive interpolation can worsen the sheet metal product for example casting character and hot-workability and ductility, so in mass, its upper limit is set to 1%.
In addition, in order to improve intensity, steel of the present invention can contain one or more among Cr, Ni, Cu, Co and the W.
Add Cr and be in order to improve intensity and the generation that suppresses carbide, in mass, addition is set to and is not less than 0.001%.But in mass, its addition surpasses 25% o'clock meeting baneful influence machinability, so above-mentioned value is confirmed as the upper limit.
Ni can be used for improving plating performance and improves intensity, in mass, confirms that Ni content is not less than 0.001%.But in mass, its addition surpasses 10% o'clock meeting baneful influence machinability, so above-mentioned value is confirmed as the upper limit.
Cu can be used for improving intensity, and in mass, the addition of Cu is not less than 0.001%.But in mass, its addition surpasses 5% o'clock meeting baneful influence machinability, so above-mentioned value is confirmed as the upper limit.
Co can be used for improving the balance between intensity and the ductility through the transformation of control plating performance and bainite, and the addition of Co is not less than 0.001%.Its upper limit is not made special regulation, still because Co is expensive element, add in a large number uneconomical, so in mass, the addition that expectation is set is not higher than 5%.
In mass, W content is defined in 0.001 to 5% scope, and its reason is: in mass, be not less than 0.001% o'clock at content, show the effect that improves intensity; But when addition surpasses 5%, can have a negative impact to machinability.
In addition, can contain among Nb, Ti, V, Zr, Hf and the Ta one or more in the steel of the present invention, they are the elements that form carbide strongly, also can be used for further improving intensity.
Above-mentioned element forms tiny carbide, nitride or carboritride and very effective to the enhancing thin steel plate.So, in mass, confirm that the needs interpolation is not less than one or more in the 0.001% above-mentioned element.On the other hand, because above-mentioned element can worsen ductility and hinder in the concentrated entering of the C retained austenite, in mass, therefore, the upper limit of total addition level is set to 1%.
Also need add B.In mass, add that to be not less than 0.0001% B be effective for strengthening crystal boundary and steel.But when in mass, its addition surpasses at 0.1% o'clock, and not only effect has reached saturated, and the increase of sheet metal intensity surpassed needs, and the result causes the deterioration of machinability, so in mass, the upper limit is set to 0.1%.
In mass, P content is defined in 0.0001 to 0.3% the scope, and its reason is: in mass, be not less than 0.0001% o'clock at content, show the effect that improves intensity; And ultralow P is unfavorable economically; When addition surpasses 0.3%, can the productivity during solderability and casting and the hot rolling be had a negative impact.
In mass, S content is defined in 0.0001 to 0.1% the scope, and its reason is: in mass, the ultralow S that is lower than lower limit 0.0001% is unfavorable economically; When addition surpasses 0.1%, can the productivity during solderability and casting and the hot rolling be had a negative impact.
P, S, Sn etc. are unavoidable impurities.In mass, expectation P content is no more than 0.05%, S content no more than 0.01% and Sn content no more than 0.01%.As everyone knows, adding little P especially is effective for the balance of improving between intensity and the ductility.
To explain that below preparation has the high-strength hot-dip galvanized steel-sheet method of above-mentioned tissue.
According to the present invention, when through hot rolling, cold rolling and annealing preparation sheet metal, cast and a kind ofly be adjusted to the bloom slab of predetermined component or after casting, cool off once, it is heated and hot rolling once more being not less than under 1180 ℃ the temperature then.At this moment, in order to suppress the formation of grain boundary oxide layer, expectation heating-up temperature again is set at and is not less than 1150 ℃ or be not higher than 1100 ℃.When heating-up temperature became very high again, oxidation squama tendency was formed uniformly on whole surface, and so just trend has suppressed the oxidation of crystal boundary.
But, can promote local oxidation when being heated to intensely when surpassing 1250 ℃ temperature, so this temperature is confirmed as the upper limit.
Low-temperature heat has postponed the formation of oxide layer self.
In addition, in order to suppress the formation of too much subscale, confirm to accomplish hot rollings being not less than 880 ℃.In order to reduce the grain boundary oxide degree of depth of product, preferably perhaps using a large amount of pickling removes surperficial squama through the high pressure descaling device after hot rolling.Afterwards, the cold rolling and annealing with sheet metal, thus obtain final products.In this case, usually the hot rolling final temperature is controlled to be and is not less than Ar
3Transition temperature, this temperature is by the decision of the chemical composition of steel, still, as long as temperature is up to than Ar
3Hang down 10 ℃ temperature approximately, final sheet metal performance of products just can not worsen.
But for fear of a large amount of formation oxidation squamas, the hot rolling final temperature is set to and is not higher than 1100 ℃.
In addition, be not less than bainite transformation point temperature through controlling cooled coiling temperature, this temperature is by the decision of the chemical composition of steel, and just can avoid too much increases load during cold rolling.But, total this and be not suitable for the very low situation of percent reduction when cold rolling, and even sheet metal batches under the transition temperature that is not higher than bainite in the steel, final sheet metal properties of product can not worsen yet.In addition; Cold rolling total reduction ratio is determined by the relation between final thickness and the cold rolling load, as long as total reduction ratio is not less than 40%, is preferably 50%; This numerical value is exactly that effectively final sheet metal properties of product can not worsen yet for reducing the grain boundary oxide degree of depth.
In the annealing process after cold rolling, when annealing temperature be lower than by the decision of the chemical composition of steel by Ac
1Temperature and Ac
30.1 * (the Ac that temperature is expressed
3-Ac
1)+Ac
1(℃) value (for example, with reference to " TekkoZairyo Kagaku ": W.C.Leslie, Supervisory Translator:Nariyasu Koda; Maruzen; P.273) time, the austenitic amount that forms during the annealing is very little, in final sheet metal, does not keep retained austenite phase or martensitic phase like this; So this value is confirmed as the lower limit of annealing temperature.Here, annealing temperature is high more, promotes that the grain boundary oxide layer that forms is many more.
Because high annealing causes promoting to form the grain boundary oxide layer, preparation cost increases, so the upper limit of annealing temperature is confirmed as Ac
3-30 (℃).Especially, annealing temperature is more near Ac
3(℃), promote that the grain boundary oxide layer that forms is many more.In this temperature range,, need be no less than 10 seconds annealing time for balance sheet metal temperature and assurance austenite.But, when annealing time surpasses 30 minutes, promoted the formation of grain boundary oxide layer and increased cost.So the upper limit was set to 30 minutes.
After this preliminary cooling is important the transition process that promotes from austenite to ferritic phase, and before transformation, comes stable austenite through the C that concentrates in mutually at austenite.
When annealing during maximum temperature be defined as Tmax (℃) time, be lower than Tmax/1000 ℃/sec.Cooling rate can bring unfavorablely in the preparation, for example cause prolonging the technological process line and significantly reduce output.On the other hand, when cooling rate surpassed Tmax/10 ℃/sec., ferritic transformation was insufficient, almost can not guarantee the retained austenite in the final sheet metal product, for example martensitic phase of a large amount of hard phases occurred.
When the maximum temperature during the annealing be defined as Tmax (℃) and up to being lower than when tentatively cooling off under Tmax-200 ℃ the temperature, produce pearlite and during cooling ferrite produce insufficient, so this temperature is confirmed as lower limit.But when preliminary cooling is surpassing when ending under Tmax-100 ℃ the temperature, ferritic transformation is insufficient, so this temperature is confirmed as the upper limit.
Be lower than 0.1 ℃/sec. cooldown rate and promote that the formation of grain boundary oxide layer is also therefore unfavorable to producing, for example cause prolonging the technological process line and significantly reduce output.So the lower limit of cooling rate is confirmed as 0.1 ℃/sec..On the other hand, when cooling rate surpassed 10 ℃/sec., ferritic transformation was insufficient, almost can not guarantee the retained austenite in the final sheet metal product, for example martensitic phase of a large amount of hard phases occurred, so the upper limit is set to 10 ℃/sec..
When up to being lower than when tentatively cooling off under 650 ℃ the temperature, cooling period can produce pearlite, causes being used for the C failure elements of stable austenite, finally can not obtain the retained austenite of sufficient quantity, so lower limit is set to 650 ℃.But when cooling is surpassing when ending under 710 ℃ the temperature, ferritic transformation is insufficient, has promoted the growth of grain boundary oxide layer, so ceiling temperature is set to 710 ℃.
In the quick cooling of the secondary cooling of successfully carrying out, cooling rate is not less than 0.1 ℃/sec. at least, preferably is not less than 1 ℃/sec., to such an extent as to during cooling, does not produce perlitic transformation, cementite deposition and analog.
But because from the angle of capacity of equipment, the cooling rate that surpasses 100 ℃/sec. almost can not realize, so the scope of cooling rate is confirmed as from 0.1 to 100 ℃/sec., and preferred from 1.0 to 100 ℃/sec..
When the cooling termination temperature of secondary cooling is lower than bath temperature, operational issue appears, and when it surpassed bath temperature+50 to+100 ℃, carbide precipitated at short notice, so, can not guarantee the retained austenite and the martensite of sufficient quantity.For these reasons, the cooling termination temperature of secondary cooling be set at from the zinc bath temperature to zinc bath temperature+50 to 100 ℃ scope.So; When guaranteeing that sheet metal transmits the stability of operation with guarantee to promote as much as possible the formation of bainite and the wettable that fully guarantees plating; Preferably sheet metal is remained on and be no less than for 1 second in the said temperature, this time is included in the dip time in the plating bath.When the retention time is long, will influence output badly and produce carbide, so, the time except annealing needs, preferably will be limited in no more than 3000 seconds the retention time.
At room temperature being retained in the austenite phase in the sheet metal for stable, is essential through the concentration of carbon that changes a part of austenite into bainite mutually and increase mutually in the austenite.In order to promote the transformation of the bainite in the Alloying Treatment process, preferably in 300 to 550 ℃ temperature range, sheet metal was kept for 1 to 3000 second, better be 15 seconds to 20 minutes.When temperature was lower than 300 ℃, the transformation of bainite took place hardly.But, when temperature surpasses 550 ℃, can form carbide, and lay in ample stocks of the retained austenite very difficulty that becomes mutually, so the upper limit is set to 550 ℃.
In order to form martensitic phase, bainite transformation need not take place, these are different with the situation that keeps the austenite phase.On the other hand; Owing under the situation that is keeping the austenite phase, must suppress carbide and pearlite formation mutually, after the secondary cooling, must fully carry out Alloying Treatment; And confirm under 300 to 550 ℃ temperature, to carry out Alloying Treatment under preferred 400 to the 550 ℃ temperature.
For the amount that guarantees oxide in the interface in above-mentioned scope, the work course of preferably controlling temperature and beginning from the hot rolling stage.At first, expectation produces surface oxide layer as far as possible equably through control: the heating-up temperature of steel slab is 1150 to 1230 ℃; 1000 ℃ percent reduction is not less than 50%; Final temperature is not less than 850 ℃, preferably is not less than 880 ℃; Coiling temperature is not higher than 650 ℃, and stays for example element such as Ti, Al at the same time.During the annealing, suppress the formation of Si oxide as much as possible in solid solution state.In addition, be desirably in final rolling after, come the oxide skin(coating) that forms during the place to go hot rolling as much as possible through high pressure descaling or a large amount of pickling.In addition, in order to weaken the generation of oxide, expectation uses diameter to be not more than the roller of 1000mm, controls cold rolling reduction ratio and is not less than 30%.Thereafter, when annealing, in order to pass through to suppress SiO
2Formation promote the formation of other oxide, expectation with the speed heating sheet metal of 5 ℃/sec. up to reaching the temperature range that is not less than 750 ℃.On the other hand, when very high or annealing time is very long when annealing temperature, produce a lot of oxides, and therefore cause machinability and fatigue resistance deterioration.So like what confirm (33) of the present invention, the maximum temperature that is desirably in annealing temperature is being not less than 0.1 * (Ac
3-Ac
1)+Ac
1(℃) to not being higher than Ac
3-30 (℃) temperature range in, control no more than 60 minutes of holdup time.
Embodiment
To come illustrated in detail the present invention based on embodiment below.
The instance 1 of embodiment 1
To at length explain the present invention based on the embodiment 1 of embodiment 1 below.
The sheet metal that will have chemical composition shown in the table 1 is heated to 1200 ℃ temperature; Be not less than Ar
3Accomplish the hot rolling of steel under the temperature of transition temperature; Cooling hot-rolled sheet metal batches sheet metal then under the temperature that is not less than bainite transformation point temperature, this temperature is by the chemical composition decision of every kind of steel; Pickling then, with the thickness of the cold rolling one-tenth of cold-rolled steel 1.0mm.
The back will mention that the trade mark is that sheet metal reduction ratio up to 1000 ℃ time of M-1, N-1, O-1, P-1 and Q-1 is 70%, final temperature is that 900 ℃ and coiling temperature are to carry out hot rolling under 700 ℃ the condition, and use diameter to carry out cold rolling as the roller of 800mm, reduction ratio with 50%.The reduction ratio of other steel up to 1000 ℃ the time is 70%, final temperature is that 900 ℃ and coiling temperature are to carry out hot rolling under 600 ℃ the condition, and uses diameter to carry out cold rolling as 1200mm roller, reduction ratio with 50%.
After this, Ac
1Transition temperature and Ac
3Transition temperature can calculate according to formula according to the composition (with quality %) of every kind of steel:
Ac
1＝723-10.7×Mn％+29.1×Si％，
Ac
3＝910-203×(C％)
1/2+44.7×Si％+31.5×Mo％-30×Mn％-11×Cr％+400×Al％。
Sheet metal carries out plating according to following condition: the speed with 5 ℃/sec. heats sheet metal up to reaching by Ac
1Transition temperature and Ac
3The annealing temperature calculated of transition temperature, and hold them in and contain 10%H
2N
2In the gas; Then, the cooldown rate with 0.1 to 10 ℃/sec. is cooled to 600 to 700 ℃ with them; Cooldown rate with 1 to 20 ℃/sec. is cooled to bath temperature continuously with them; They are immersed in 460 ℃ the zinc plating bath reached for 3 seconds, wherein, solution composition changes.
In addition, when carrying out the Fe-Zn Alloying Treatment, be adjusted to 5-20% in mass, in 300 to 550 ℃ temperature range, kept 15 seconds to 20 minutes then with some sheet metal plating and with the Fe content in the coating.State through dregs coalescence on the visual observation surface is assessed plating performance with the area of measuring the plating leakage part.Through coating being dissolved in 5% the hydrochloric acid solution that contains corrosion inhibiter and this solution being carried out chemical analysis confirm Coating composition.
Intercepting is used to carry out the JIS#5 sample (reduction ratio with 0.5 to 2.0% is rolled at the skin-pass line) of tension test and measures its mechanical performance from the plating sheet metal.In addition, through in the plain bending fatigue test, apply the pressure that is equivalent to 50% hot strength and come assessment rupture life relatively.In addition, through the assessment of salt spray test repeatedly corrosion resisting property.
As shown in table 2, in steel of the present invention, the degree of depth of grain boundary oxide layer is very shallow, and under the pressure that is equivalent to 50% hot strength, surpass 10 fatigue life
6Individual bend cycles.In addition, well balance intensity and ductility, do not observe the rust product, even after test, keep good appearance yet.
Table 3-1 (continuing): the plating performance of various steel
| The code of steel-processing numbering | The content % of Al in the coating | The content % of Mn in the coating | The content % of Fe in the coating | The calculated value of formula (1) | Other element % in the coating |
| C-1 | 1 | 1 | 15 | 1.77 | ? |
| C-2 | 0.5 | 0.01 | 7 | -4.35 | ? |
| E-1 | 0.05 | 0.5 | 12 | 7.76 | ? |
| E-1-1 | 0.17 | 0.04 | 9 | 0.51 | Si：0.02 |
| E-1-2 | 0.18 | 0.03 | 9 | 0.26 | Y：0.02， Nd：0.04 |
| E-1-3 | 0.17 | 0.03 | 9 | 0.38 | La：0.02 |
| E-1-4 | 0.15 | 0.02 | 9 | 0.51 | B：0.005 |
| E-1-5 | 0.2 | 0.08 | 9 | 0.63 | Rb：0.02 |
| E-2 | 0.25 | 0.01 | 8 | -0.87 | ? |
| G-1 | 0.3 | 0.3 | 11 | 2.05 | ? |
| G-2 | 0.2 | 0.01 | 8 | -0.33 | ? |
| H-1 | 0.5 | 0.5 | 7 | 1.26 | ? |
| I-1-1 | 0.1 | 0.05 | 7 | 0.63 | CS：0.04 |
Table 3-2 (continuing): the plating performance of various steel
| The code of steel-processing numbering | The content % of Al in the coating | The content % of Mn in the coating | The content % of Fe in the coating | The calculated value of formula (1) | Other element % in the coating |
| I-1-2 | 0.15 | 0.1 | 8 | 0.63 | K：0.02， Ni：0.05 |
| I-1-3 | 0.14 | 0.1 | 7 | 0.76 | Ag：0.01， Co：0.01 |
| I-1-4 | 0.3 | 0.25 | 8 | 0.63 | Ni：0.02， Cu：0.03 |
| I-1-5 | 0.35 | 0.27 | 9 | 0.26 | Na：0.02， Cr：0.01 |
| I-2 | 0.5 | 0.1 | ? | -3.74 | ? |
| J-1 | 1 | 1 | ? | 0.24 | ? |
| J-2 | 1 | 1 | 8 | 0.24 | ? |
| J-3 | 0.5 | 0 | 4 | -6.02 | ? |
| K-1-1 | 1 | 0.9 | ? | 0.69 | Be：0.005 |
| K-1-2 | 0.8 | 0.7 | ? | 0.69 | Ti：0.01， In：0.01 |
Table 3-3 (continuing): the plating performance of various steel
| The code of steel-processing numbering | The content % of Al in the coating | The content % of Mn in the coating | The content % of Fe in the coating | The calculated value of formula (1) | Other element % in the coating |
| K-1-3 | 0.9 | 0.8 | ? | 0.69 | Cd：0.02 |
| K-2-1 | 0.9 | 0.8 | 9 | 0.69 | Pb：0.03 |
| K-2-2 | 1 | 0.95 | 8 | 1.32 | To：0.02 |
| K-2-3 | 1 | 0.9 | 8 | 0.69 | W：0.02， Hf：0.02 |
| L-1-1 | 0.3 | 0.15 | 10 | 0.60 | Mo：0.01 |
| L-1-2 | 0.25 | 0.14 | 10 | 1.10 | Zr：0.01， Ti：0.01 |
| L-1-3 | 0.3 | 0.2 | 9 | 1.23 | Ge：0.01 |
| L-1-4 | 0.3 | 0.15 | 11 | 0.60 | Ta：0.01， V：0.01 |
| M-1 | 0.3 | 0.4 | 11 | 3.73 | ? |
| N-1 | 0.4 | 0.3 | 11 | 1.23 | ? |
| O-1 | 0.5 | 0.5 | 12 | 2.48 | ? |
| P-1 | 0.1 | 0.3 | 11 | 4.98 | ? |
| Q-1 | 0.15 | 0.2 | 10 | 3.10 | ? |
Table 3-4 (continuing): the plating performance of various steel
| The appearance of plating leakage defective | Outward appearance after the salt spray test repeatedly | Remarks |
| No | Non-corrosive | Steel of the present invention |
| Have | Get rusty | Comparative steel |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| Have | Get rusty | Comparative steel |
| No | Non-corrosive | Steel of the present invention |
| Have | Get rusty | Comparative steel |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
Table 3-5 (continuing): the plating performance of various steel
| The appearance of plating leakage defective | Outward appearance after the salt spray test repeatedly | Remarks |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| Have | Get rusty | Comparative steel |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| Have | Get rusty | Comparative steel |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
Table 3-6 (continuing): the plating performance of various steel
| The appearance of plating leakage defective | Outward appearance after the salt spray test repeatedly | Remarks |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
| No | Non-corrosive | Steel of the present invention |
Surplus element in (remarks) coating is a zinc.
The numeral of underscoring is a situation about dropping on outside the scope of the invention.
Even be appreciated that under the situation that sheet metal, contains a large amount of Si, in sheet metal of the present invention,, also can make sheet metal not form the plating leakage defective and have good corrosion resistance through control coating and steel-sheet composition from table 3.
In addition, be appreciated that when containing the 4th kind of element (in the table 3 " other element in the coating ") in the coating that even under the very little situation of the definite value in the left side of formula 1, plating performance is also fine.
Table 4 has shown the influence of preparation condition.Do not satisfy at the steel-sheet working condition under the situation of said requirement,, thereby shortened fatigue life even its composition in said scope, also can make the degree of depth of grain boundary oxide layer become big.In addition, be appreciated that it promptly is to satisfy said requirement conversely, depart from the sheet metal composition under the situation of said scope, also can make fatigue life also very short at working condition.
Table 5 has shown the influence of oxide form.In sheet metal of the present invention, do not form rust and fatigue strength and surpass 2 * 10
6Individual bend cycles is so sheet metal has good material quality.
The instance 1 of embodiment 2
To at length explain the present invention based on the embodiment 1 of embodiment 2 below.
The sheet metal that will have chemical composition as shown in table 6 is heated to 1200 ℃ temperature; Be not less than Ar
3Accomplish the hot rolling of steel under the temperature of transition temperature; With hot rolled steel sheet cooling, sheet metal to be batched being not less than under the temperature of bainite transformation point then, this temperature is determined by the chemical composition of every kind of steel; Pickling then is with the cold rolling one-tenth thickness of this sheet metal cold-reduced sheet that is 1.0mm.
After this, Ac
1Transition temperature and Ac
3Transition temperature with the composition (with quality %) of every kind of steel, calculate according to formula:
Ac
1＝723-10.7×Mn％-16.9×Ni％+29.1×Si％+16.9×Cr％，
Ac
3＝910-203×(C％)
1/2+15.2×Ni％+44.7×Si％+104×V％+31.5×Mo％-30×Mn％-11×Cr％-20×Cu％+700×P％+400×Al％+400×Ti％。
This sheet metal carries out plating through following step: sheet metal is heated to by Ac
1Transition temperature and Ac
3The annealing temperature calculated of transition temperature, and hold them in and contain 10%H
2N
2In the gas; Then, the cooldown rate with 0.1 to 10 ℃/sec. is cooled to 680 ℃ with them; Cooldown rate with 1 to 20 ℃/sec. is cooled to bath temperature continuously with them; They are immersed in 460 ℃ the zinc plating bath reached for 3 seconds, wherein, solution composition changes.
In addition, when carrying out the Fe-Zn Alloying Treatment, some sheet metals kept 15 seconds to 20 minutes in 300 to 550 ℃ temperature range after zinc-plated, and the Fe content in the coating is adjusted to 5 to 20% in mass.State through dregs coalescence on the visual observation surface is assessed plating performance with the area of measuring the plating leakage part.Through coating being dissolved in 5% the hydrochloric acid solution that contains corrosion inhibiter and this solution being carried out chemical analysis confirm Coating composition.
Intercepting is used to carry out the JIS#5 sample (reduction ratio with 0.5 to 2.0% is rolled at the skin-pass line) of tension test and measures its mechanical performance from the plating sheet metal.Then, after applying 20% stretcher strain, through sheet metal is applied 60 ° of bendings and backward bending forming assess the adhesion of coating behind the severe deformation.Through the polyethylene insulation band being attached to the part of carrying out behind crooked and the bending forming backward and it being peeled off the adhesion of assessment coating relatively, measure in the per unit length ratio of the length that comes off then.Preparation condition is shown in Table 8.
As shown in table 7, at sheet metal of the present invention, promptly; D1 to D8 (Nos.1,2,5 to 8; 10 to 14) under the situation, do not observe the plating leakage defective, well balance intensity and ductility; Even and after applying 20% stretcher strain, apply crooked and bending forming backward to sheet metal, the ratio that comes off of coating also is low to moderate and is no more than 1%.On the other hand, in comparative steel, that is, and under the situation of C1 to C5 (numbering 17 to 21), in order to prepare test specimen, crack in a large number during the hot rolling and productivity ratio very low.After the hot rolled steel sheet that is obtained through polishing was removed crackle, the cold rolling and annealing with this hot rolled steel sheet was used as the quality of materials test then.But the adhesiveness of some sheet metals (C2 and C4) after fierce operation is very poor or be unable to bear 20% shaping.
As shown in table 8, in the numbering that does not satisfy formula 13,9,19 and 21, deterioration of coating wettable and the binding force of cladding material behind severe deformation are very poor.The steel-sheet microscopic structure is being adjusted under the unsafty situation, and the plating adhesion after the fierce operation is also very poor.
Under the situation of numbering 4, because the secondary cooldown rate is very slow, thus do not produce austenite and martensite, but the generation pearlite in generation and the plating adhesion after the fierce operation are very poor.
The embodiment 1 of embodiment 3
To at length explain the present invention based on the embodiment 1 of embodiment 3 below.
The sheet metal that will have chemical composition shown in the table 9 is heated to 1200 ℃ temperature; Be not less than Ar
3Accomplish the hot rolling of steel under the temperature of transition point; With hot rolled steel sheet cooling, batch sheet metal being not less than under the temperature of bainite transformation point then, this temperature is determined by the chemical composition of every kind of steel; Pickling then, with the cold rolling one-tenth thickness of this sheet metal cold-reduced sheet that is 1.0mm.
After this, Ac
1Transition temperature and Ac
3Transition temperature according to the composition (with quality %) of every kind of steel, calculate according to formula:
Ac
1＝723-10.7×Mn％+29.1×Si％，
Ac
3＝910-203×(C％)
1/2+44.7×Si％+31.5×Mo％-30×Mn％-11×Cr％+400×Al％。
This sheet metal carries out plating through following step: sheet metal is heated to by Ac
1Transition temperature and Ac
3The annealing temperature calculated of transition temperature, and hold them in and contain 10%H
2N
2In the gas; Then, the cooldown rate with 0.1 to 10 ℃/sec. is cooled to 680 ℃ with them; Cooldown rate with 1 to 20 ℃/sec. is cooled to bath temperature continuously with them; They are immersed in 460 ℃ the zinc plating bath reached for 3 seconds, wherein, solution composition changes.
In addition, when carrying out the Fe-Zn Alloying Treatment, some sheet metals kept 15 seconds to 20 minutes in 300 to 550 ℃ temperature range after zinc-plated, and the Fe content in the coating is adjusted to 5 to 20% in mass.State through dregs coalescence on the visual observation surface is assessed plating performance with the area of measuring the plating leakage part.Through coating being dissolved in 5% the hydrochloric acid solution that contains corrosion inhibiter and this solution being carried out chemical analysis confirm Coating composition.
Intercepting is used to carry out the JIS#5 sample (reduction ratio with 0.5 to 2.0% is rolled at the skin-pass line) of tension test and measures its mechanical performance from galvanized sheet metal.Then, after applying 20% stretcher strain, through sheet metal is applied 60 ° of bendings and backward bending forming assess the adhesion of coating behind the severe deformation.Through the polyethylene insulation band being attached to the sweep that carries out behind crooked and the bending forming backward and it being peeled off the adhesion of assessment coating relatively, measure in the length that per unit length comes off the ratio of the length that comes off then.Preparation condition is shown in Table 11.
As shown in table 10, at sheet metal of the present invention, that is, and D1 to D12 (Nos.1,2; 5,12,13,20,22 to 24; 32,34 to 36,39 and 42) under the situation, do not observe the plating leakage defective; Well balance intensity and ductility, even and after applying 20% stretcher strain, apply crooked and bending forming backward to sheet metal, the ratio that comes off of coating also is low to moderate and is no more than 1%.In addition, be appreciated that when containing other element as shown in table 10 in the coating that even under the situation less by the determined value in formula 1 left side, plating performance is also fine.
On the other hand, in comparative steel, that is, and under the situation of C1 to C5 (numbering 44 to 48), in order to prepare test specimen, crack in a large number during the hot rolling and productivity ratio very low.After the hot rolled steel sheet that is obtained through polishing was removed crackle, the cold rolling and annealing with this hot rolled steel sheet was used as the quality of materials test then.But the adhesiveness of some sheet metals (C2 and C4) after fierce operation is very poor or be unable to bear 20% shaping.
As shown in table 10, in the numbering that does not satisfy formula 13,21,46 and 48, deterioration of coating wetability and the adhesiveness after fierce operation are very poor.The steel-sheet microscopic structure is being adjusted under the unsafty situation, and the plating adhesion after severe deformation is also very poor.
Under the situation of No.3, because the secondary cooldown rate is very slow, thus do not produce austenite and martensite, but the generation pearlite and the plating adhesion after severe deformation in generation are very poor.
The embodiment of embodiment 2
To at length explain the present invention based on the embodiment of embodiment 2 below.
The sheet metal that will have chemical composition as shown in table 12 is heated to 1180 to 1250 ℃ temperature; 880 to 1100 ℃ of hot rollings of accomplishing steel down; With hot rolled steel sheet cooling, batch sheet metal being not less than under the temperature of bainite transformation point then, this temperature is determined by the chemical composition of every kind of steel; Pickling then is with the cold rolling one-tenth thickness of this sheet metal cold-reduced sheet that is 1.0mm.
After this, Ac
1Transition temperature and Ac
3The composition (with quality %) of every kind of steel of transition temperature root a tree name, calculate according to formula:
Ac
1＝723-10.7×Mn％+29.1×Si％，
Ac
3＝910-203×(C％)
1/2+44.7×Si％+31.5×Mo％-30×Mn％-11×Cr％+400×Al％。
This sheet metal carries out plating through following step: sheet metal is heated to by Ac
1Transition temperature and Ac
3The annealing temperature calculated of transition temperature, and they be retained in contain 10%H
2N
2In the gas; Then, the cooldown rate with 0.1 to 10 ℃/sec. is cooled to 650 to 700 ℃ temperature range with them; Cooldown rate with 0.1 to 20 ℃/sec. is cooled to bath temperature continuously with them; They are immersed in 460 to 470 ℃ the zinc plating bath reached for 3 seconds, wherein, solution composition changes, and the reduction ratio with 0.5 to 2.0% is rolled on the skin-pass line.
In addition, when carrying out the Fe-Zn Alloying Treatment, some sheet metals kept 15 seconds to 20 minutes in 400 to 550 ℃ temperature range behind plating, and the Fe content in the coating is adjusted to 5 to 20% in mass.State through dregs coalescence on the visual observation surface is assessed plating performance with the area of measuring the plating leakage part.Through coating being dissolved in 5% the hydrochloric acid solution that contains corrosion inhibiter and this solution being carried out chemical analysis confirm Coating composition, the result is shown in Table 13.
In the table 13 and 14, the evaluation grade of all outward appearances that satisfies the steel of formula (2) among the present invention all is 5, well balance intensity and ductility.On the other hand, the comparative steel of discontented unabridged version invention prescribed limit, its outward appearance evaluation grade is low without any exception, the balanced differences of intensity and ductility.In addition, be produced the steel that drops in the claim prescribed limit of the present invention, its microscopic structure is made up of above-mentioned tissue, and the balance between the outward appearance of steel and intensity and the ductility is good.
Table 13-1-1: coating wetability, corrosion resistance, microscopic structure and the fatigue life of various steel.
| The code of steel | Handle numbering | Mn content in the coating, % | Al content in the coating, % | Mo content in the coating, % | Fe content in the coating, % | (1) value of calculating by formula |
| A | 1 | 0.01 | 0.1 | 0.0001 | ? | 0.43 |
| A | 2 | 0.05 | 0.15 | 0.001 | 12 | 0.38 |
| A | 3 | 0.04 | 0.6 | 0.001 | 11 | -0.07 |
| B | 4 | 0.03 | 0.3 | 0.001 | ? | 0.141 |
| B | 5 | 0.11 | 0.4 | 0.002 | 10 | 0.041 |
| B | 6 | 0.04 | 0.4 | <0.0001 | ? | 0.041 |
| C | 7 | 0.1 | 0.3 | 0.002 | 12 | 0.245 |
| C | 8 | 0.04 | 0.8 | 0.003 | 11 | -0.26 |
| D | 9 | 0.7 | 0.5 | <0.0001 | ? | 0.051 |
| D | 10 | 0.6 | 0.4 | 0.002 | 10 | 0.151 |
| E | 11 | 0.2 | 0.3 | 0.005 | 11 | 0.205 |
| E | 12 | 0.15 | 0.4 | 0.002 | 10 | 0.105 |
| E | 13 | 0.3 | 0.3 | 0.005 | 10 | 0.205 |
| F | 14 | 0.5 | 0.45 | 0.001 | ? | 0.046 |
| F | 15 | 0.1 | 0.05 | 0.003 | 9 | 0.446 |
Table 13-1-2 (continuing): coating wetability, corrosion resistance, microscopic structure and the fatigue life of various steel.
| The code of steel | Handle numbering | Mn content in the coating, % | Al content in the coating, % | Mo content in the coating, % | Fe content in the coating, % | (1) value of calculating by formula |
| G | 16 | 1 | 0.5 | 0.002 | 10 | 0.025 |
| G | 17 | 1 | 0.4 | 0.002 | 10 | 0.125 |
| H | 18 | 0.5 | 0.7 | 0.0003 | ? | -0.19 |
| H | 19 | 0.4 | 0.35 | 0.0002 | 10 | 0.165 |
| H | 20 | 0.5 | 0.45 | 0.0002 | 9 | 0.065 |
| I | 21 | 0.7 | 0.1 | 0.001 | 11 | 0.442 |
| I | 22 | 0.7 | 0.5 | 0.003 | 12 | 0.042 |
| I | 23 | 1 | 0.4 | 0.002 | 12 | 0.142 |
| I | 24 | 0.05 | 0.45 | 0.004 | 11 | 0.092 |
| I | 25 | 0.5 | 0.3 | 0.007 | 12 | 0.242 |
| I | 26 | 0.5 | 0.35 | 0.001 | ? | 0.192 |
| I | 27 | 0.6 | 0.13 | <0.0001 | ? | 0.412 |
| J | 28 | 0.05 | 0.34 | 0.0002 | 11 | 0.118 |
?
Table 13-1-4 (continuing): the fatigue life of the coating profit warm nature of various steel, corrosion resistance, microscopic structure.
| Other elements in the coating, % | , plating whether applies alloying heat treatment after handling | The outward appearance evaluation grade | ? |
| ? | Not | 5 | Steel of the present invention |
| ? | Be | 5 | Steel of the present invention |
| ? | Be | 3 | Comparative steel |
| ? | Not | 5 | Steel of the present invention |
| Si：0.001 | Be | 5 | Steel of the present invention |
| ? | Not | 3 | Comparative steel |
| ? | Be | 5 | Steel of the present invention |
| ? | Be | 2 | Comparative steel |
| Cr：0.004， W：0.005 | Not | 3 | Comparative steel |
| Cr：0.005， W：0.007 | Be | 5 | Steel of the present invention |
| K：0.01 | Be | 5 | Steel of the present invention |
| Ag：0.004 | Be | 5 | Steel of the present invention |
| Ni：0.01， Cu：0.01， Co：0.002 | Be | 5 | Steel of the present invention |
| Ti：0.002， CS：0.003 | Not | 5 | Steel of the present invention |
| Rb：0.002 | Be | 5 | Steel of the present invention |
Table 13-1-5 (continuing): coating wetability, corrosion resistance, microscopic structure and the fatigue life of various steel.
| Other elements in the coating, % | , plating whether applies alloying heat treatment after handling | The outward appearance evaluation grade | ? |
| V：0.003， Zr：0.003， Hf：0.002， Ta：0.002 | Be | 5 | Steel of the present invention |
| V：0.002， Zr：0.002， Nd：0.007 | Be | 5 | Steel of the present invention |
| B：0.002， Y：0.003 | Not | 3 | Comparative steel |
| B：0.003， Y：0.002 | Be | 5 | Steel of the present invention |
| Na：0.007 | Be | 5 | Steel of the present invention |
| Cd：0.01 | Be | 5 | Steel of the present invention |
| La：0.02 | Be | 5 | Steel of the present invention |
| Tl：0.02 | Be | 5 | Steel of the present invention |
| In：0.005 | Be | 5 | Steel of the present invention |
| Be：0.01 | Be | 5 | Steel of the present invention |
| Pb：0.02 | Not | 5 | Steel of the present invention |
| ? | Not | 4 | Comparative steel |
| ? | Not | 5 | Steel of the present invention |
?
The embodiment of embodiment 3
To at length explain the present invention based on the embodiment of embodiment 3 below.
The sheet metal that will have chemical composition as shown in Tble 15 is heated to 1200 to 1250 ℃ temperature; Be not less than under 1000 ℃ the temperature, to be not less than the steel roughing of total reduction ratio of 60% heating; Accomplish the steel-sheet hot rolling then; With the cooling of this hot rolled steel sheet, batch this sheet metal under the temperature of bainite transformation point being not less than then, this temperature is determined by the chemical composition of every kind of steel; Pickling then, with the cold rolling one-tenth thickness of this sheet metal cold-reduced sheet that is 1.0mm.
After this, Ac
1Transition temperature and Ac
3Transition temperature according to the composition (with quality %) of every kind of steel, calculate according to formula:
Ac
1＝723-10.7×Mn％+29.1×Si％，
Ac
3＝910-203×(C％)
1/2+44.7×Si％+31.5×Mo％-30×Mn％-11×Cr％+400×Al％。
This sheet metal carries out plating through following step: sheet metal is heated to by Ac
1Transition temperature and Ac
3The annealing temperature calculated of transition temperature, and hold them in and contain 10%H
2N
2In the gas; When the highest obtainable temperature during the annealing be defined as Tmax (℃) time, cool off in Tmax-200 ℃ to Tmax-100 ℃ temperature range with the cooldown rate of Tmax/1000 to Tmax/10 ℃/sec. annealing back; Then, with the cooldown rate of 0.1 to 100 ℃/sec., in the temperature range of bath temperature-30 ℃ to bath temperature+50 ℃, cool off; Then, they are immersed in the plating bath; In the temperature range of bath temperature-30 ℃ to bath temperature+50 ℃, kept 2 to 200 seconds, this time comprises dip time.When carrying out Fe-Zn Alloying Treatment, some sheet metals plating after, 400 to 550 ℃ temperature range in kept 15 second to 20 minute, and Fe content in coating in mass be adjusted to 5 to 20% thereafter.In addition, be rolled on the skin-pass line with 0.5 to 2.0% reduction ratio.Sheet metal is carried out sufficient flat wise bend (R=1t),, in containing the environment of chlorine, carry out up to the cyclic corrosion test of 150 JASO circulations and the progress of evaluation of corrosion as the corrosion proof mode of assessment.Through coating being dissolved in 5% the hydrochloric acid solution that contains corrosion inhibiter and this solution being carried out chemical analysis confirm Coating composition, the result is shown in Table 16.
In the table 16 and 17, all corrosion evaluation grades that satisfy the steel of formula (3) among the present invention all are 4 or 5, well balance intensity and ductility.
On the other hand, the comparative steel of discontented unabridged version invention prescribed limit is because it can not satisfy microscopic structure or to the control of preparation condition, the balance between its intensity and ductility is poor without any exception.The corrosion evaluation grade of comparative steel numbering 3,13 and 20 is 4 or 5.But, numbering 13 and 20, the balance between its intensity and ductility is very poor, and the tensile strength of numbering 3 is very low.In addition, what make drops on the steel in the claim prescribed limit of the present invention, and its microscopic structure is made up of above-mentioned tissue, and the balance between the outward appearance of steel and intensity and the ductility is good.
Industrial applicibility
The present invention provides: a kind of sheet metal with high strength, high ductibility galvanizing by dipping sheet metal and galvanizing by dipping layer DIFFUSION TREATMENT of high antifatigue and highly corrosion resistant; Binding force of cladding material after the high-strength hot-dip galvanized sheet metal that a kind of ductility is excellent, this sheet metal can improve the plating leakage defective and improve severe deformation, and preparation method thereof; A kind of high-strength high-tractility galvanizing by dipping sheet metal with high antifatigue and highly corrosion resistant; The high-strength hot-dip galvanized sheet metal that a kind of outward appearance and additivity are excellent, this sheet metal can suppress the plating leakage generation of defects, and preparation method thereof; A kind of high strength, through sheet metal and a kind of high-strength hot-dip galvanized sheet metal of galvanizing by dipping layer DIFFUSION TREATMENT; This sheet metal can suppress plating leakage defective, blemish and have corrosion resistance; The corrosion resistance in containing the environment of chlorion particularly; Have simultaneously high ductibility again, with and preparation method thereof.
Claims (6)
1. the sheet metal of the galvanizing by dipping layer DIFFUSION TREATMENT of the high-strength high-tractility with highly corrosion resistant, the surface of thin steel sheet of said galvanizing by dipping layer DIFFUSION TREATMENT has one deck coating, and in mass, this coating contains,
Al:0.001～4%, and
Fe：5％～20％，
Surplus is zinc and unavoidable impurities, and in mass, sheet metal contains:
C：0.0001～0.3％，
Si:0.001～less than 0.1%,
Mn：0.001～3％，
Al：0.001～4％，
Mo：0.001～1％，
P：0.001～0.3％，
S:0.0001～0.1%, and
Surplus is Fe and unavoidable impurities, it is characterized in that, in the coating in Al quality % content A and Mo quality % content B and the steel Mo quality % content C satisfy formula 3; And the microscopic structure of steel comprises that by accounting for 3 volume % to 50 volume % that 50 volume % to 97 volume % comprise principal phase and the surplus of ferrite or ferrite and bainite the complex tissue of martensite or martensite and retained austenite forms:
100≥(A/3+B/6)/(C/6)≥0.01 3。
2. the sheet metal of the galvanizing by dipping layer DIFFUSION TREATMENT of the high-strength high-tractility with highly corrosion resistant as claimed in claim 1; It is characterized in that the austenite of formation sheet metal second phase and/or martensitic average grain size are 0.01 to 0.6 times of ferrite average grain size.
3. galvanizing by dipping sheet metal with high-strength high-tractility of highly corrosion resistant, said galvanizing by dipping surface of thin steel sheet has one deck coating, and in mass, this coating contains,
Al:0.001～4%, and
Fe: be lower than 5%,
Surplus is zinc and unavoidable impurities, and in mass, sheet metal contains:
C：0.0001～0.3％，
Si:0.001～be lower than 0.1%,
Mn：0.001～3％，
Al：0.001～4％，
Mo：0.001～1％，
P：0.001～0.3％，
S:0.0001～0.1%, and
Surplus is Fe and unavoidable impurities, it is characterized in that, in the coating in Al quality % content A and Mo quality % content B and the steel Mo quality % content C satisfy formula 3; And the microscopic structure of steel comprises that by 50 volume % to 97 volume % 3 volume % to 50 volume % of principal phase and the surplus of ferrite or ferrite and bainite comprise that the complex tissue of martensite or martensite and retained austenite forms:
100≥(A/3+B/6)/(C/6)≥0.01...3。
4. the galvanizing by dipping sheet metal with high-strength high-tractility of highly corrosion resistant as claimed in claim 3; It is characterized in that the austenite of formation sheet metal second phase and/or martensitic average grain size are 0.01 to 0.6 times of ferrite average grain size.
5. sheet metal or claim 3 or 4 described galvanizing by dipping steel-sheet methods that are used to prepare the galvanizing by dipping layer DIFFUSION TREATMENT of claim 1 or 2 described high-strength high-tractilities with highly corrosion resistant with high-strength high-tractility of highly corrosion resistant; The sheet metal of the galvanizing by dipping layer DIFFUSION TREATMENT of said high-strength high-tractility with highly corrosion resistant or the galvanizing by dipping sheet metal with high-strength high-tractility of highly corrosion resistant have fabulous corrosion resistance; It is characterized in that the steel casting that will comprise like each said chemical composition among the claim 1-4 obtains bloom slab; And then heat above-mentioned bloom slab and reach 1200 to 1300 ℃; With total reduction ratio of 60 to 99%, under 1000 to 1150 ℃ temperature, the heated bloom slab of roughing is with the preparation hot rolled steel sheet then; Pickling and cold rolling hot rolled steel sheet then; Then, be not less than in ℃ 0.12 * (Ac
3-Ac
1)+Ac
1To be not higher than in ℃ Ac
3In+50 the temperature range, with above-mentioned cold-reduced sheet annealing 10 seconds to 30 minutes; Then, after the annealing, the highest annealing temperature in the time will annealing be defined as in ℃ Tmax the time, with the cooldown rate of Tmax/1000-Tmax/10 ℃/sec, above-mentioned sheet metal is cooled to Tmax-200 ℃ to Tmax-100 ℃ temperature range; Then, with the cooldown rate of 0.1～100 ℃/sec, above-mentioned sheet metal is cooled in the temperature range of bath temperature-30 ℃ to bath temperature+50 ℃; Then sheet metal is immersed in the plating bath; Sheet metal is remained in the temperature range of bath temperature-30 ℃ to bath temperature+50 ℃ and reach 2 to 200 seconds, the above-mentioned time comprises dip time; Afterwards, above-mentioned sheet metal is cooled to room temperature.
6. method as claimed in claim 5 is characterized in that after sheet metal being immersed in the zinc plating bath, carries out Alloying Treatment at 300 to 550 ℃, then sheet metal is cooled to room temperature.
Applications Claiming Priority (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP170857/2001 | 2001-06-06 | ||
| JP2001170857 | 2001-06-06 | ||
| JP2001211942 | 2001-07-12 | ||
| JP211942/2001 | 2001-07-12 | ||
| JP2001304035 | 2001-09-28 | ||
| JP304036/2001 | 2001-09-28 | ||
| JP2001304036A JP3898924B2 (en) | 2001-09-28 | 2001-09-28 | High-strength hot-dip galvanized steel sheet excellent in appearance and workability and its manufacturing method |
| JP304034/2001 | 2001-09-28 | ||
| JP304035/2001 | 2001-09-28 | ||
| JP304037/2001 | 2001-09-28 | ||
| JP2001304034A JP3898923B2 (en) | 2001-06-06 | 2001-09-28 | High-strength hot-dip Zn-plated steel sheet excellent in plating adhesion and ductility during high processing and method for producing the same |
| JP2001304037A JP3898925B2 (en) | 2001-09-28 | 2001-09-28 | High strength and high ductility hot dip galvanized steel sheet excellent in corrosion resistance and method for producing the same |
| JP131643/2002 | 2002-05-07 | ||
| JP2002131643A JP4331915B2 (en) | 2001-07-12 | 2002-05-07 | High strength and high ductility hot dip galvanized steel sheet excellent in fatigue durability and corrosion resistance and method for producing the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028115236A Division CN100562601C (en) | 2001-06-06 | 2002-06-06 | Have the high-strength hot-dip galvanized steel sheet of high binding force of cladding material behind fatigue resistance, erosion resistance, ductility and the severe deformation and the steel sheet and the manufacture method thereof of galvanizing layer DIFFUSION TREATMENT |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101125473A CN101125473A (en) | 2008-02-20 |
| CN101125473B true CN101125473B (en) | 2012-07-18 |
Family
ID=39093643
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710140271 Expired - Lifetime CN101264681B (en) | 2001-06-06 | 2002-06-06 | Hot-dip galvannealed steel sheet, steel sheet treated by hot-dip galvannealed layer diffusion and a method of producing the same |
| CN2007101402736A Expired - Lifetime CN101125473B (en) | 2001-06-06 | 2002-06-06 | Hot-dip galvanized thin steel sheet, thin steel sheet processed by hot-dip galvanized layer, and a method of producing the same |
| CN 200710140272 Expired - Lifetime CN101125472B (en) | 2001-06-06 | 2002-06-06 | Hot-dip galvanized thin steel sheet, thin steel sheet processed by hot-dip galvanized layer, and a method of producing the same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710140271 Expired - Lifetime CN101264681B (en) | 2001-06-06 | 2002-06-06 | Hot-dip galvannealed steel sheet, steel sheet treated by hot-dip galvannealed layer diffusion and a method of producing the same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710140272 Expired - Lifetime CN101125472B (en) | 2001-06-06 | 2002-06-06 | Hot-dip galvanized thin steel sheet, thin steel sheet processed by hot-dip galvanized layer, and a method of producing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN101264681B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5776959B2 (en) * | 2009-12-18 | 2015-09-09 | 日立金属株式会社 | Die steel with excellent hot workability |
| CN101748353B (en) * | 2009-12-28 | 2012-02-15 | 江苏麟龙新材料股份有限公司 | Method for antiseptic treatment of marine climate resistant engineering component |
| TWI479028B (en) * | 2011-09-30 | 2015-04-01 | Nippon Steel & Sumitomo Metal Corp | High-strength galvanized steel sheet having high tensile strength at a maximum tensile strength of 980 MPa and excellent in formability, high-strength alloyed hot-dip galvanized steel sheet and method of manufacturing the same |
| JP5994356B2 (en) | 2012-04-24 | 2016-09-21 | Ｊｆｅスチール株式会社 | High-strength thin steel sheet with excellent shape freezing property and method for producing the same |
| CN104520448B (en) * | 2012-06-05 | 2017-08-11 | 蒂森克虏伯钢铁欧洲股份公司 | The manufacture method of steel, flat product and the flat product |
| JP6470266B2 (en) * | 2013-05-17 | 2019-02-13 | エーケー スティール プロパティ−ズ、インク． | Galvanized steel for press hardening and method for producing the same |
| CN104164627B (en) * | 2014-07-25 | 2016-05-25 | 合肥市瑞宏重型机械有限公司 | A kind of running roller high strength alloy steel and manufacture method thereof |
| CN104258788B (en) * | 2014-09-19 | 2016-10-05 | 常熟市联明化工设备有限公司 | Chemical industry equipment reactor |
| KR101561008B1 (en) * | 2014-12-19 | 2015-10-16 | 주식회사 포스코 | Hot dip galvanized and galvannealed steel sheet having higher hole expansion ratio, and method for the same |
| CN105369162A (en) * | 2015-12-16 | 2016-03-02 | 常熟市凯波冶金建材机械设备厂 | Anti-explosion gas turbine housing |
| CN105986174A (en) * | 2015-12-28 | 2016-10-05 | 合肥中澜新材料科技有限公司 | Corrosion-resisting alloy stirring tank body |
| CN107142438B (en) * | 2017-06-28 | 2019-11-08 | 过冬 | A kind of hot galvanizing antioxidant and its preparation method and application |
| CN107641685B (en) * | 2017-10-14 | 2019-10-15 | 广西盛隆冶金有限公司 | A kind of heat treatment method of high-strength steel sheet |
| CN108048775B (en) * | 2018-01-11 | 2020-10-20 | 江苏刚正薄板科技有限公司 | Preparation method of strong corrosion-resistant hot-dip magnesium-aluminum-zinc plated plate |
| EP3856936B1 (en) * | 2018-09-26 | 2022-08-24 | ThyssenKrupp Steel Europe AG | Method for producing a coated flat steel product and coated flat steel product |
| CN110273111B (en) * | 2019-07-30 | 2020-11-24 | 马鞍山钢铁股份有限公司 | Zinc-based coating hot forming steel with wide hot forming heating process window and preparation method thereof |
| MX2022004360A (en) * | 2019-10-11 | 2022-05-03 | Jfe Steel Corp | High-strength steel sheet, shock-absorbing member, and method for producing high-strength steel sheet. |
| MX2022004359A (en) * | 2019-10-11 | 2022-05-03 | Jfe Steel Corp | High-strength steel sheet, impact absorbing member, and method for manufacturing high-strength steel sheet. |
| CN113249649B (en) * | 2021-04-16 | 2022-10-21 | 首钢集团有限公司 | Cold-rolled high-strength steel with good coating quality and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2259920A (en) * | 1991-09-10 | 1993-03-31 | Gibson Chem Ltd | Surface conversion coating solution based on molybdenum and phosphate compounds |
| CN1099429A (en) * | 1993-06-29 | 1995-03-01 | 日本钢管株式会社 | Surface treated steel sheet and method therefor |
| US5474658A (en) * | 1992-02-22 | 1995-12-12 | Hoechst Ag | Electrochemical process for preparing glyoxylic acid |
| US6004507A (en) * | 1997-08-11 | 1999-12-21 | Alphatech, Inc. | Material formulation for galvanizing equipment submerged in molten and aluminum zinc melts |
| CN1286730A (en) * | 1998-09-29 | 2001-03-07 | 川崎制铁株式会社 | High strength thin steel sheet, high strength alloyed hot-dip zinc-coated steel sheet, and method for producing them |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0328359A (en) * | 1989-06-23 | 1991-02-06 | Kawasaki Steel Corp | Production of hot-dip aluminized chromium-containing steel sheet |
| CA2256667A1 (en) * | 1996-05-31 | 1997-12-04 | Kawasaki Steel Corporation | Plated steel sheet |
-
2002
- 2002-06-06 CN CN 200710140271 patent/CN101264681B/en not_active Expired - Lifetime
- 2002-06-06 CN CN2007101402736A patent/CN101125473B/en not_active Expired - Lifetime
- 2002-06-06 CN CN 200710140272 patent/CN101125472B/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2259920A (en) * | 1991-09-10 | 1993-03-31 | Gibson Chem Ltd | Surface conversion coating solution based on molybdenum and phosphate compounds |
| US5474658A (en) * | 1992-02-22 | 1995-12-12 | Hoechst Ag | Electrochemical process for preparing glyoxylic acid |
| CN1099429A (en) * | 1993-06-29 | 1995-03-01 | 日本钢管株式会社 | Surface treated steel sheet and method therefor |
| US6004507A (en) * | 1997-08-11 | 1999-12-21 | Alphatech, Inc. | Material formulation for galvanizing equipment submerged in molten and aluminum zinc melts |
| CN1286730A (en) * | 1998-09-29 | 2001-03-07 | 川崎制铁株式会社 | High strength thin steel sheet, high strength alloyed hot-dip zinc-coated steel sheet, and method for producing them |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平6-57448A 1994.03.01 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101125472A (en) | 2008-02-20 |
| CN101125472B (en) | 2013-04-17 |
| CN101264681A (en) | 2008-09-17 |
| CN101125473A (en) | 2008-02-20 |
| CN101264681B (en) | 2013-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100562601C (en) | Have the high-strength hot-dip galvanized steel sheet of high binding force of cladding material behind fatigue resistance, erosion resistance, ductility and the severe deformation and the steel sheet and the manufacture method thereof of galvanizing layer DIFFUSION TREATMENT | |
| CN101125473B (en) | Hot-dip galvanized thin steel sheet, thin steel sheet processed by hot-dip galvanized layer, and a method of producing the same | |
| JP3527092B2 (en) | High-strength galvannealed steel sheet with good workability and method for producing the same | |
| CA2879069C (en) | Galvanized steel sheet for hot forming | |
| CN102378824B (en) | High-strength hot-dip galvanized steel plate and method for producing same | |
| EP2762590A1 (en) | Galvanized steel sheet and method of manufacturing same | |
| JP3898923B2 (en) | High-strength hot-dip Zn-plated steel sheet excellent in plating adhesion and ductility during high processing and method for producing the same | |
| JP3921136B2 (en) | High strength and high ductility hot dip galvanized steel sheet with excellent burring workability and manufacturing method thereof | |
| KR101899688B1 (en) | High strength hot-rolled steel sheet having excellent continuously producing property, high strength gavanized steel sheet having excellent surface property and plating adhesion and method for manufacturing thereof | |
| CA3082357A1 (en) | A method for the manufacturing of liquid metal embrittlement resistant zinc coated steel sheet | |
| JP3731560B2 (en) | Steel plate with excellent workability and shape freezing property and its manufacturing method | |
| JP4331915B2 (en) | High strength and high ductility hot dip galvanized steel sheet excellent in fatigue durability and corrosion resistance and method for producing the same | |
| JP3921135B2 (en) | High strength and high ductility hot dip galvanized steel sheet with excellent burring workability and manufacturing method thereof | |
| JP7215518B2 (en) | HOT PRESS MEMBER AND MANUFACTURING METHOD THEREOF | |
| US20230392226A1 (en) | Hot-pressed member, steel sheet for hot pressing, and methods for producing the hot-pressed member and the steel sheet for hot pressing | |
| JP4148235B2 (en) | Steel plate with excellent workability and shape freezing property and its manufacturing method | |
| JPH10158784A (en) | High strength hot rolled steel sheet | |
| JP7215519B2 (en) | HOT PRESS MEMBER AND MANUFACTURING METHOD THEREOF | |
| JP3921101B2 (en) | Manufacturing method of high strength and high ductility hot dip galvanized steel sheet with excellent shape freezing property | |
| JPH11315360A (en) | Galvannealed steel sheet excellent in plating adhesion, and its manufacture | |
| JP3875958B2 (en) | High strength and high ductility hot dip galvanized steel sheet with excellent workability and manufacturing method thereof | |
| JP2004232065A (en) | Hot dip galvanized steel sheet, and production method therefor | |
| WO2023074115A1 (en) | Hot-pressed member |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: NIPPON STEEL + SUMITOMO METAL CORPORATION Free format text: FORMER NAME: SHIN NIPPON STEEL LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan Patentee after: Nippon Steel Corporation Address before: Tokyo, Japan Patentee before: Nippon Steel Corporation |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan Patentee after: Nippon Iron & Steel Corporation Address before: Tokyo, Japan Patentee before: Nippon Steel Corporation |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20120718 |